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ABSTRACT
TRIORGANOSILICON s¥DIKETONATES.
ENOL ETHER ISOMERISM AND STEREOCHEMICAL LABILITY
by Ward T. Collins

A series of triorganosilicon acetylacetonates of the
type R(CH3)ZSi(acac) (R =‘g-C4Ha, cans, CH2=CH, CFSCHaCHa,
and cans), along with (05H5)2(CH3)Si(acac), has been
prepared by reaction of the appropriate triorganochloro-
silane and acetylacetone in the presence of pyridine. The
compounds possess open-chain enol ether structures and
give rise to configurations in which the uncoordinated
carbonyl oxygen atom is positioned both gig and E£é2§ to
the siloxy group. Equilibrium values of the g;§_to
§r§n§_ratios'in chlorobenzene are dependent on the nature
of the substituents on silicon and lie in the range 0.25 -
0.39. The gig isomers undergo a rapid intramolecular
rearrangement process which interchanges the allylic and
acetyl methyl groups on the acetylacetonate moiety.

First order rate constants in chlorobenzene solution

were determined by nmr line broadening methods, and the
results were compared with those reported for (CH3)3Si(acac).
In the gig_- R(CHe)2Si(acac) series of compounds the
lability increases in the order R =‘Q-C4Ha < 02H5 < CH3 <
CH2=CH'< can; < CF30H20H2. The lability of g;§_- (cans);-
(CH3)Si(acac) is comparable to that‘of-gig,- (CF3CH20H2)-
(CH3)2Si(acac). The kinetic data are consistent with a

mechanism involving formation of a five-coordinated
silicon intermediate.

Trimethylsilyl derivatives of dipivaloylmethane
(Hdpm) and hexafluoroacetylacetone (H hfac) have also
been prepared and studied briefly. On the basis of
infrared and nmr studies, it is suggested that (CH3)3Si-
(dpm) exists almost exclusively as the gig enol ether
isbmer and undergoes a rapid stereochemical rearrangement
which averages the nonequivalent t,- C‘H9 environments
on the nmr time scale even at -95°C. 0n the other hand,
(CH3)3Si(hfac) appears to adopt only the m enol

ether configuration in solution.

TRIORGANOSILICON B-DIKETONATES.
ENOL ETHER ISOMERISM AND STEREOCHEMICAL LABILITY

By

If;
a OK
’1

‘0 0"
Ward T. Collins

A THESIS

Submitted to
Michigan State University
in partial fulfillment of the requirements
for the degree of

MASTER OF SCIENCE
Department of Chemistry

1970

DEDICATION

To my Parents

11

ACKNOWLEDGEMENTS

I wish to thank Dow Corning Corporation for their
financial assistance and encouragement throughout my
graduate studies.

I also wish to thank Dr. Cecil L. Frye who encouraged
‘my initial interest in silicon chemistry and Dr. Thomas J.
Pinnavaia for his guidance and assistance during the course

of this work.

111

iI

TABLE OF CONTENTS

Page
Dedication 11
Acknowledgements iii
Table of Contents iv
List of Tables vii
List of Figures viii
Introduction 1
Experimental 6
A. Reagents and General Technique 6
B. Preparation of Compounds 7
l. Triorganosilylacetylacetonates 7

a. Butyldimethylsilylacetylacetonate

b. Ethyldimethylsilylacetylacetonate

c. Vinyldimethylsilylacetylacetonate

d. Phenyldimethylsilylacetylacetonate

e. Diphenylmethylsilylacetylacetonate

f. Trifluoropropyldimethylsilylacetyl-

acetonate
2. 1,1,l,5,5,5-Hexafluoro-2-trimethylsiloxy-

2-pentene-4-one 7

3. 2,2,6,6-Tetramethyl-3-trimethylsiloxy-

3-heptene-5-one 9

#. Trimethylsiloxy-2-pentene-4-one 10

C. Instrumentation ll
1. Infrared Spectroscopy 11

2. Proton Magnetic Resonance Spectroscopy 11

iv

TABLE OF CONTENTS - Continued

III

IV

Page
3. Mass Spectrometry l2
4. Chromatography 12
D. Preparation of Solutions for NMR Study 12
Results and Discussion 14
A. Preparation of Compounds 1%
B. Mass Spectra 15
C. Infrared Spectra 18
D. NMR Spectra 21
E. NMR Line Broadening Studies 29
Appendixes
A. Mass Spectra #4
l. Butyldimethylsilylacetylacetonate
2. Ethyldimethylsilylacetylacetonate
3. Trimethylsilylacetylacetonate
A. Vinyldimethylsilylacetylacetonate
5. Trifluoropropyldimethylsilylacetyl-
acetonate
6. Phenyldimethylsilylacetylacetonate
. Diphenylmethylsilylacetylacetonate
. 1,1,l,5,5,5-Hexafluoro-2-trimethyl-
siloxy-2-pentene-4-one
9. 2,2,6,6-Tetramethyl-3-trimethylsiloxy-
3-heptene-5-one
B. Infrared Spectra 54

1.

Butyldimethylsilylacetylacetonate

TABLE OF CONTENTS - Continued

Page
Ethyldimethylsilylacetylacetonate
Trimethylsilylacetylacetonate
Hexafluoroacetylacetone
1,1,1,5,5,S-Hexafluoro-trimethyl-
siloxy—2-pentene-h-one
Dipivaloylmethane
2,2,6,6-Tetramethyl-3-trimethyl-

siloxy-3-heptene-5-one

C. Proton NMR Spectra 62

l.
2.
3.
A.
5.
6

7.

Butyldimethylsilylacetylacetonate
Ethyldimethylsilylacetylacetonate
Trimethylsilylacetylacetonate
Vinyldimethylsilylacetylacetonate
Phenyldimethylsilylacetylacetonate
Trifluoropropyldimethylsilylacetyl-
acetonate

Diphenylmethylsilylacetylacetonate

Bibliography 42

vi

LIST OF TABLES
Table Page
I Synthesis and Analytical Data 8
II Intensities of Selected Ions in the Mass
Spectra of Triorganosilicon Acetylacetonates 16
III Selected Stretching Frequencies (cm'l) for
Silyl Enol Ethers and Related Compounds 19
IV Proton Chemical Shift Data for gig: and Trans:
Triorganosilicon Acetylacetonates 23
V Equilibrium Ratio of gig and Trans Enol Ether
Isomers for Triorganosilicon Acetylacetonates 27
VI Nmr Line Shape Parameters for the Acetyl-
acetonate Methyl Resonance of gingriorgano-
silicon Acetylacetonates 3#
VII Kinetic Data for Acetylacetonates Methyl Group
Exchange in Cis-Triorganosilicon Acetyl-
acetonates 36
VIII Taft Parameters for Methyl Group Euchange
in gigrR(CH3)2Si(acac) Derivatives in Chloro-

benzene Solution 39

vii

LIST OF FIGURES
Figure Page
1 Exchange-Broaden Acetylacetonate Methyl 32
Proton Resonances for gingriorganosilicon
Acetylacetonates in Chlorobenzene
2 Log k/k°X§_o* Plot at 25° for Methyl Group 40
Exchange in Qig-R(CH3)2Si(acac) Derivatives

in Chlorobenzene

viii

I. INTRODUCTION

The first silicon derivative of acetylacetone was
reported by Dilthey1 in 1903. He found that the product
obtained by reaction of 51014 and acetylacetone,
[H(acac)] had the emperical formula C15H2203C1281.
Dilthey proposed a'siliconium ion containing three
chelated acetylacetonate groups and a hydrogen dichloride
anion, [Si(acac)3][HCla]. A number of other tris(2,h-
pentadionato)siliconium salts with other anions were
also prepared.

More recently, additional s-ketonate chelate
derivatives have been reported. Pike and Luongo2 found
that if organocarboxysilanes are used instead of silicon
tetrachloride in the reaction with acetylacetone, then
a neutral chelated.silane Species is produced which con—

tains only two chelated acetylacetonate ligands.

 

H l
Si(OC-CH3)4 + H300 - CH=C-CH3 CHC13 >

H3C
:C_'j_0 (1):

HC f_ _ Si(OC-CH3)2 + CHSCOOH.
\ -

c - o
HgC/

2

The authors were able to identify both gi§_and trans
octahedral isomers hv nmr spectrOSCOpy. It is of

interest to point out that when they carried out the
reaction at O - 5°, a product with the same empirical

formula was obtained. In this case, however, the two

2,A-pentanedionato ligands were believed to be mono-
dentate, producing a tetravalent silicon(IV) derivative.
These structural assignments were based solely on
infrared spectroscopic analysis which show very charac-
teristic bonds for the chelated and non-chelated deriva-
tives of acetylacetone. A similar compound, Si(acac)2-
C12, has recently been obtained by Thompson3 from the
reaction of equimolar quantities of acetylacetone and
.silicon tetrachloride in methylene chloride solution.
The compound was insoluble in most organic solvents and
only sparingly soluble in chloroform and methylene
chloride. The compound rearranges in solution to give
Si(C5H702)3Cl and 5101,. The mpg-configuration was
assigned to the Si(acac)2012 compound on the basis of
‘nmr data.

In most of the compounds described so far the s-
diketonate is bonded to the metal through both donor.
oxygens, forming a cyclic chelate structure. In certain
silyl-s-diketonates"°, however, the ligand is bonded
through only one oxygen, resulting in a linear enol
ether structure with an uncoordinated carbonyl group.

Knoth‘ prepared a series of trialkylsilyl enol
ethers (I) O

R3810C=CHCR
R

(I)

by reaction of a trialkyl chlorosilane and a s-diketone.

-3...

In spite of the favorable geometry of the s-carbonyl
oxygen to coordination to silicon, it was shown by
infrared spectroscopy that in none of the compounds did
the carbonyl oxygen coordinate to form a pentacoordinate
silicon(IV) complex. It was further suggested that in
the case of (CH3)SSi(acac) both gig and giggg (II and III)

isomers existed in equilibrium.

o§\§
c-cna H
I
(CH3)3Si-O c (CH3)3Si-O c o
c . ‘3
CH3 CH3 CH3
II III
cis trans

2-(Trimethylsiloxy)-4-ketopentene

The identification of both the gig and giggg isomers
was based on the coincidence of infrared absorption
bands for the compound and the carbonyl stretching fre-
quencies of the gig and giggg methyl enol ethers of
acetylacetone7. It is of interest to point out that
the equilibrated methyl enol ether is almost pure £3323
isomer.

The non-chelated structure of 2-(trimethylsiloxy)-
A-ketopentene was confirmed independently in a study by
Wests. This work consisted of preparing a number of
acetylacetoxy substituted silanes both chelated and non-

chelated, and showing that these two classes of silanes

have very characteristic infrared absorption bands

The chelated silicon compounds did not show a carbonyl
absorption in the region near 1700 cm'l, but the
absorption was shifted to gg, 1555 cm". The non-
chelated compounds on the other hand showed two strong
bonds near 1670 and 1590 cm'l, which are characteristic
frequencies for a normal carbonyl stretching vibration
and a C=C stretch, respectively.

The presence of gig and giggg isomers of (CH3)3-
Si(acac) has recently been confirmed by nuclear magnetic
resonance spectroscopya. Howe and Pinnavaia also found
that the gig isomer undergoes a novel stereochemical
rearrangement process whereby the two methyl groups of
the s-diketonate ligand are rapidly exchanging on the
silane moiety through a chelated pentacoordinate inter-

rnediate or transition state

0 CH3(2)
\C‘CH3(2) /O.: C/\
Rasi-O c ..-——'-—-="-—- R381 ‘; C-H
\C/ \H \O';’(‘3’/
\
6113(1) CH3(1)
O§§§
C‘CH3(1)
'
-—4> R Si-O C
<— 3 \C/ \H

-5-

“Values of first order rate constants in chlorobenzene
solution gave an Arrhenius activation energy of 13.81 I
0.64 kcal/mole, and a pre-experimental factor of exp.
(13.052 i .538)1°.

The present study is concerned with the preparation
and characterization of a series of new silyl enol ethers
of acetylacetone. The effect of silicon substituents
on the stereochemistry and stereochemical lability of
the compounds has been investigated. Silyl enol ethers
of other s-diketones have also been prepared in order to
assess the effect of the polarity of the terminal
,groups on the diketonate ligand on the stereochemistry

and lability .

II. EXPERIMENTAL

A. Reagents and General Techniques

All of the chlorosilanes were obtained from the
Dow Corning Research Department. These silanes were
obtained as pure chemicals or were fractionally dis-
tilled to a purity of 98% or better, as determined by
vapor phase chromatography. The hexane used as a
solvent was Fisher Certified A.C.S. Grade solvent.
Prior to each reaction the solvent was freshly dis-
tilled from CaHa. Matheson, Coleman and Bell (M.C.B.)
dioxane was refluxed over sodium for 24 hours and then
'was distilled. Pyridine was Baker Analyzed Reagent
Grade and was stored over Drierite. M.C.B. white
label acetylacetone was freshly redistilled before use.
:30damide was purchased from K and K Laboratories Inc.
sand was handled in a nitrogen filled glove bag. The
areaction flasks were fitted with a reflux condenser and
aa pressure-compensating addition funnel. The reaction
rnedium was stirred with a magnetic stir-bar. All re-
aactions were run under a dry nitrogen atmosphere to
rminimize hydrolysis. Reactions which yielded pyridinium
(fliloride or sodium chloride as a by-product were filtered
111 a closed system under vacuum. All product distillations

warns conducted ig vacuo or in a dry nitrogen atmosphere.

B. Preparation of Compounds

1. Triorganosilylacetyiacetonates

The triorganosiloxyacetylacetonates were prepared
by a procedure reported by Weste. The following is a
general description of the technique used. The exact
experimental conditions for the individual compounds
are listed in Table I.

A solution of 0.25 moles of pyridine, 0.25 moles
of acetylacetone and 100 ml. of hexane was treated with
0.25 moles of a triorganochlorosilane over a 5 to 10
minute period. The solution was refluxed from zero to
five hours and then stirred at room temperature for an
additional 12 to 2A hours. The reaction medium was
vacuum-filtered to remove pyridinium chloride and was
continuously evacuated until all of the hexane solvent
‘was removed. The crude products were distilled in a
high vacuum or at reduced pressure in a nitrogen
atmosphere. The boiling points of the products along
*with the yields and analytical data are also listed in
{Table I. The phenyl-substituted siloxyacetylacetonates
Ivere not refluxed during their preparation because of
apparent slow decomposition at elevated temperatures.
Emphasis was placed primarily on obtaining pure compounds

aJld not on maximiZing yields.

2. iii,i,5,545-Hexafluoro-2-trimethyisiloxy-2-
pentene-A-One

A solution of 11.7 g. (0.056 moles) hexafluoro-

acertylacetone and 20 ml. of trimethylchlorosilane was

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

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heated at reflux temperature for eleven days in a dry-
nitrogen atmosphere. Gas-liquid chromatographic analysis
indicated that approximately 90% of the hexafluoroacetyl-
acetone remaining had undergone silylation. Presumably,
some of the free ligand had evaporated through the reflux
condenser. The reaction mixture was distilled through a
6 inch vacuum-Jacketed Vigreaux column at atmospheric
pressure in a closed, dry system to give 6.7 g. (42%
yield) of pure enol ether, b.p. 128 - 129°. The com-
‘pound is a pale yellow liquid.

Anal. Calcd. for CngoF30281: c, 36.0; H, 3.57;
_F. 40.7; Si, 10.0. Found: C, 34.9; H, 4.01; F, 40.6;
Si, 10L9%.

3. 2 2,6,6-Tetramethy1-3-trimethylsiloxy-3-hgptene-

Earls
No reaction was observed between dipivaloyl-

methane and trimethylchlorosilane in the presence of
pyridine at room temperature. It was necessary to prepare
'the sodium derivative of the s-diketone and to allow the
salt to react with the chlorosilane.

Sodium dipivaloylmethanate was prepared by slowly
adding dipivaloylmethane (9.40 g., 0.04 mole) to a
Slurry of sodamide (1.6u g., 0.04 mole) in 40 ml. of
dioxane in a nitrogen atmOSphere. The hazy light yellow
solution was heated at reflux temperature for 20 minutes
to remove as much ammonia as possible. Trimethylchloro-

silane (5.90 g., 0.0540 moles) was added dropwise to

-10-

the hot solution. During the addition finely divided
sodium chloride precipitated from the solution. The
reaction mixture was stirred for 10 hours at room tem-
perature and then was heated at reflux temperature for
an additional hour. The sodium chloride could not be
completely removed by filtration, presumably, because
of .ts fine particle size or slight solubility in
dioxane. Consequently it was necessary to remove the
dioxane solvent by evacuation, and to dilute the product
with hexane before the sodium chloride was completely
removed by filtration. The hexane was removed by
evacuation and the product was distilled in high vacuum
(b.p. 45°/0.04 mm.), producing 5.24 g. (51.2% yield)
of colorless liquid.

Anal. Calcd. for C14H220281: C, 65.6; H, 11.0;
Si, 11.0. Found: c, 66.2; H, 11.2; Si, 11.6.

4. 2-Trimeggylsiloxy—2—pentene-4-one

This compound was also prepared by using the

same sodamide technique described for the»dipivaloyl-
methane derivative. Nuclear magnetic resonance spectro-
scopic analysis of the crude product confirmed that the
‘gig_and giggg forms of the desired compound are present
in their equilibrium ratio and that silylation occurred

at an oxygen atom and not at the central carbon atom

in the p-diketone.

-11-

C. Instrumentation
1. Infrared Spectroscogy
The infrared spectra were obtained with a Perkin-
Elmer 521 Spectrometer by using a 0.1 mm path length
cell. The following dilutions, solvents and cells were

used for the designated infrared regions:

3800 - 3100 cm'1 10% solution in 001., NaCl cell
1300 - 650 cm'1 2% solution in 032, NaCl cell
650 - 250 cm"1 10% solution in 001,, CsBr cell

2. Proton Magnetic_Resonance Spectroscopy
Proton magnetic resonance spectra were obtained

with a varian A56/60D analytical spectrometer operated
at 60.000 M Hz. The probe temperature was controlled to
i 0.5° with a varian Model V-604O temperature controller.
Temperatures were determined by measuring the chemical
shift differences between the proton resonances of methanol
or ethylene glycol and applying the equations of van Geet‘z.
Magnetic field sweep widths were calibrated by the audio-
frequency side band technique. At least three spectral
copies were averaged in the determination of line shape
‘parameters and chemical shift values in order to reduce
any error caused by variations in the field sweep. A11
Spectra were recorded at a ratio-frequency field strength
well below the value necessary to observe the onset of
saturation.

The spectrum of Measi(dpm) also was obtained on a

‘Varian HA-lOO spectrometer operating at 100 MHZ.

-12-

3. Mass Spectrometry
The mass spectra were obtained with an Associated
Electrical Industries MS-12. The following experimental
conditions were used to obtain all spectra: inlet tem-
perature (all glass heated) 135 to 138°; source temperature
115 to 180°; accelerating voltage 8 k.v.; trap current
100 microamps; ionizing potential 80 electron volts.
Perfluorokerosene was used to calibrate the instrument.
4. Chromatography
Attempts were made to separate the gig,and giggg
isomers of (CH3)3Si(acac) on a dual-column F and M Model
810 gas chromatograph equipped with a thermal conductivity
detector cell. The column dimension and packings were as
follows: 4 ft. x 1/4 in., 10% silmethylene on Chromasorb
W; 6 ft. x 1/4 in., F8 1265 fluorosilicone gum on an
unknown Chromasorb; 6 ft. x 1/4 in., SE-30 silicone
rubber on Chromasorb W. Numerous chromatograms were
obtained under isothermal and temperature-programmed
column conditions in the temperature range 100 - 300°.
In all cases there was no separation of the two isomers.
Attempts to separate the isomers on 20 ft. carbowax
columns at 150 - 180° with an Aerograph A 90-P3 chromato-
graph were also unsuccessful.
D. Eggparation of Solutions for NMR Stugy
All solutions used in the nmr studies were pre-
pared in a nitrogen-filled Glove Bag and sealed in nmr

tubes which had been previously dried at 150° and cooled

-13-

in a calcium sulfate desiccator. Carbon tetrachloride,
benzene, and chlorobenzene were dried by refluxing over
calcium hydride for at feast 48 hours. Despite these
precautions to avoid hydrolysis, small amounts (2 - 3%)
of free acetylacetone and (Rasi)20 could be detected in
the nmr spectrum of the Solutions after they had aged
several days at room temperature. Presumably, these
triorganosilicon acetylacetonates undergo slow re-
action with hydroxyl groups or strongly bound water on
the surface of the glass nmr tubes. The rates of
stereochemical rearrangements of the gig_isomers, however,
showed no dependence on the concentration of hydrolysis

products.

-14-

III. RESULTS AND DISCUSSION

A. Preparation of Compounds

A series of triorganosilicon enol ethers 0f acetyl-
acetone of the type R(CH3)2Si(acac) (where R = groans,
02115, CH2 =CH, CF30H2CH2 and 0.115), along with
(CQH5)2(CH3)Si(acac), has been prepared by reaction of
the appropriate triorganoohlorosilane and acetylacetone
in the presence of pyridine, according to the procedure
reported by West°

R33101 + H(acac)' +- py -—> Rasi(acac) + [py H]Cl

(1)

The previously reported compound (CH3)3Si(acac)°”

was
obtained from J. J. Howél°. The compounds were obtained
as high boiling colorless to pale yellow liquids. All
undergo hydrolysis on contact with atmospheric moisture
and slow thermal decomposition at elevated temperatures.
Attempts to prepare trimethylsilicon hexafluoroacetyl-
acetonate, (CH3)3Si(hfac), and dipivaloylmethanate,
(CH3)3Si(dpm), by reactions analogous to reaction (1) were
unsuccessful. With hexafluoroacetylacetone the reaction
mixture yielded only pyridinium hexafluoroacetylacetonate,
as identified by infrared spectroscopy. In the case of
dipivaloylmethane, no reaction products were observed.
However, (CH3)3Si(hfac) was obtained by heating at
.reflux temperature for Several days the free ligand in a

large excess of (CH3)38101.

-15-

(CH3)33101 + H(hfa0) e2: (CH3)3Si(hfac) + H01
(2)

The equilibrium represented by reaction (2) was displaced
to the right by the evolution of gaseous HCl from the
reaction mixture. To prepare the dipivaloylmethane
derivative it was necessary to first form the sodium salt
of the diketone, followed by the reaction of the salt
with (0H3)3Si01.’

NaNHa +- H(dpm) -—> Na(dpm) + NH3 (3)

Na(dpm) + (CH3)3SiCl -—> (0Ha)381(dpm) + NaCl (A)
An analogous reaction sequence was also successful for
the preparation of (CH3)gSi(acac).
B. mass Spectra

Each of the silyl enol ethers of acetylacetone gave
a mass spectral fragmentation pattern consistent with an
open chain enol ether structure. In the R(CH3)2Si(acac)
series silicon containing fragments of the type
R(CH3)2Si+, (CH3)§Si(acac)+ and R(CH3)Si(acac)+ were
generally formed in appreciable amounts. The relative
intensities of these ions are collected in Table II
along with the intensity of the most abundant organic
species. A weak molecular ion peak was observed for the
compounds with R = CaHs, CH3, CH2=CH and CF3CH2CH2.
The absence of a molecular ion peak for the derivative
with R =‘g - C4He and CeHs is attributed to the facile

loss of g.- butyl and methyl groups, respectively, from

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-17-

the parent ions. It is noteworthy that (CF30H20H2)-
(CH3)2Si(acac) undergoes extensive rearrangement upon
electron impact to give ions with mass values corresponding
to (CH3)2Si+F and (CH3)SiF2+, SiF3+ and (0H3)Si(acac)F+
with intensities of 59.8, 7.6, 93.5 and 14.1 respectively.
Some degree of rearrangement probably occurs for the other
compounds in the R(CH3)2Si(acac) series, because weak

to moderately intense peaks were observed in all cases

at mass 45, 59 and 75, which correspond to (CH3)SiH2+,
(CH3)2SiH+ and (CH3)2SiOH+.

The mass spectrum of (CaH5)2(CH3)Si(acac) did not
contain a molecular ion peak. The fragment 02H30+ was
observed as the base ion and (CeH5)CH351(acac)+ was the
most abundant silicon-containing fragment. Numerous re-
arrangement fragments were observed in the spectrum,
but in all cases their relative intensitites were less
than 3.0.

In the spectrum of (CH3)3Si(hfac), the base ion was
the rearrangement fragment (CH3)2SiF+. Another rearrange-
ment fragment present in appreciable abundance was
(CH3)2SiOH+ with an intensity of 28.3. Intense peaks
were also observed for the parent ion minus CFa (13.9),
CF34“ (58.3) and (CH3)331+ (77.2).

For (CH3)3Si(dpm) the mass spectrum showed a very
weak parent ion at m/e = 256 with an intensity of 0.3,
and a base peak at m/e = 199, which corresponds to the

loss of a butyl group from the parent ion. Intense lines

-18-

were observed for (CH3)381+, C4H9+, and (CH3)2Si(dpm)+
with intensities of 46.3, 26.5 and 23.8, respectively.
Silicon-containing rearrangement fragments were found for
masses corresponding to (CH3)2SiOH+, (CH3)2SiH+ and
(CH3)SiH2+, with intensities of 15.7, 1.4 and 6.8,
respectively.

Complete mass spectra for all of silyl enol ethers
studied are tabulated in Appendix A.
C. Infrared Spectra

Several of the compounds prepared in this study were
investigated by infrared Spectroscopy. The C = 0 and
C = C and Si — 0 stretching frequencies for the silyl
enol ethers are summarized in Table III along with the
C = 0 and C = C vibrations of the chelated copper(II)
complexes and the enol forms of acetylacetone, hexa-
fluoroacetylacetone, and dipivaloylmethane. Complete
spectra are shown in Appexdix B.

Knoth‘ has reported that (CH3)3Si(acac) gives rise
to two uncoordinated carbonyl stretching frequencies
at 1656 and 1683 cm-1, which he assigned to the gig (II)
and 33.293 (III) enol ether isomers, respectively. These
vibration frequencies were coincident with the carbonyl
stretching vibrations of the gig and giggg methyl enol
ethers of acetylacetone. The less intense, lower energy
band.at 1656 cm"1 was assigned to the gig_isomer on the
basis that this would be the least favored conformation

for steric reasons. The nmr studies reported below

Table III. - Selected Stretching Frequencies (cm-1) for

-19-

Silyl Enol Ethers and Related Compounds

 

 

 

Compound v(C=0) v(C=C) v(Si-O)

Qg-C4H9){CH3)2Si(acac) 1685, 1664 1590, 1625 1032

(C235)(CH3)ZSi(acac) 1682, 1660 1588, 1621 1034

(CH3)¢Si(acac) 1684, 1659 1588, 1625 1032

J

[Si(acac)3][HC12]-a- 1555 ?

, b

Lu(acac)2- 1580 1554

H(acac), enolE- 1620 1620

(CH3)3Si(hfac) 1733 1625 945
d

Cu(hfac)2_ 1652 1620

H(hfac), enol 1684 1627

(CH3)3Si(dpm) 1676 1625 1100

Cu(dpm)23 1552 1500

H(dpm), enol W1610 N1575

3 Ref. 8 9 Ref. 12 9—Ref. 13 2Ref. 14.

-20-

confirm that the gig isomer is the less abundant form.
All of the Rasi(acac) compounds listed in Table III
exhibited two carbonyl stretching frequencies. Following
Knoth, we assign the lower energy band to the gi§_isomer
and the higher energy band to the trans isomer. Two
C = C stretching vibrations are also observed in the
region 1588 - 1625 cm-1. Based on relative intensities,
the higher energy C a C band is assigned to the gig,
isomer. Unlike the acetylacetonate derivatives, (CH3);-
Si(hfac) and (CH3)3Si(dpm) each exhibit only one c - o
and one C a C stretching frequency. This result is in
agreement with the nmr data presented below which
suggest that these two compounds exist almost exclusively
as a single isomer. The chelated compounds [Si(acac)3]-
[H0132], Cu(acac)2, Cu(hfac)2 and Cu(dpm)a are listed
in Table III to illustrate that the C - 0 and C - C
stretching modes occur at much lower energy in the
chelates than in the enol ethers. The fact that the
carbonyl stretching frequency for the chelated Cu(hfac)a
is at higher frequency than the other chelated compounds
results from the electron withdrawing influence of the
fluoromethyl groups. This same effect is evident in the
spectrum of (CH3)aSi(hfac) where the non-chelated carbonyl
stretch is shifted’to much higher energy than the other
diketonate derivatives.

For neat (CH3)3Si(acac), West° assigned the Si-O
stretching vibration at 1020 cm“. In the R331(acac)

-21-

compounds investigated here, the vibration was observed
at 1032 - 1034 cm'1 in CCI. solution. The assignment of
the 81-0 stretching frequency for (CH3)3Si(hfac) and
(CH3)381(dpm) is nOt straightforward because no strong
unique bands are observed for these compounds in the
1000 - 1050 region where one normally expects the vibration
to occur. In the case of (CH3)3Si(hfac), however, there
is a strong band at lower frequency, 962 cm'l, which
may result from motion of the 81-0 group. This assignment
is made on the baSis of the inductive effect of the
terminal CFa groups on the diketonate ligand weakening
the 81-0 bond strength. 'Similarly, the inductive effect
of the terminal trbutyl groups in (CH3)3Si(dpm) would be
expected to shift the Si-O vibration to higher energy.
Thus, the 1,100 cm"1 band in (CH3)38i(dpm) is tentatively
assigned to the Silo vibration.
D. W

The existence Of an equilibrium mixture of gi§_(II)
and 3322.9. (III) enol ether isomers for (CH3)SSi(acac) has
been previously confirmed by nmr spectroscopy”. Analogous
isomers exist for the new silyl derivatives prepared in
the present work. The proton nmr spectrum of each trans
isomer contains a uCH- multiplet, two acetylacetonate
methyl doublets, and a Si-CHa singlet. Splitting of the
acetylacetonate methyl proton lines results from spin-
spin coupling between the =CH- proton and both methyl
groups. The =CH-, acetylacetonate methyl, and Si-CH3

-22-

regions of the nmr Spectra of the gi§_isomers each contain
one resonance line. The presence of only one acetyl-
acetonate methyl resonance for the gig isomers is due to
rapid intramolecular rearrangement processes which inter-
change the non-equivalent acetyl and allylic methyl groups
on the acetylacetonate moiety. The rearrangement is
believed to occur via a penta-coordinated silicon inter-
mediate or transition state”. A similar process for the
trans isomers is restricted by lack of rotation about the C=C
bond. The rates of rearrangement are discussed in

detail in Section III D.

2)
0 CH3(
\C‘CH3(2) O—C
R810 0 RSi/d--“\CH
3 - / \ —_—h 3 ‘_—’l .-
\c/ 1H \o—c:
'
CH3(1) CH3(1)
o
§§
C-CH3(1)
I
A -
<____ R3810\C/C\H
0H3(2)

Chemical shifts in carbon tetrachloride for the
acetylacetonate and Si-CHa protons of the Rgsi(acac)
compounds are collected in Table IV; shifts for
(CH3)SSi(acac) in benzene and as the neat liquid are
included for comparison. No significant concentration
dependence was observed for (CH3)3Si(acac) in carbon

tetrachloride over the range 2.0 - 3.0 g/100 ml of solvent.

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-24-

Since some concentration dependence was found in benzene,
the shifts in this solvent were extrapolated to infinite
dilution. In each trans isomer the magnitude of the
coupling between the =CH- and COCHg protons is approxi-
mately 0.6 Hz, and the aIlylic coupling constant is 0.4 Hz
or less. It is to be noted that the relative chemical
shifts for the C0CH3 and =CCH3 protons of the trans
isomers are not in-agreement with the empirical "ene-
one“ rule of Anteunis and Schamp16 for assigning chemical
shifts of similar types of protons in s-diketone enol
ethers. However, at least three pieces of evidence can
be cited in support of the assignments made here:

(1) Replacement of alkyl groups on silicon by phenyl
groups leads to 0.09 - 0.14 ppm up-field shifts for the
=CCH3 protons, whereas the COCH3 and =CH protons show
little or no change in chemical shift. An examination

of molecular models of the t§§g§_phenylsilyl derivatives
reveals that reasonable configurations are possible in
which the =CCH3 protons are within the diamagnetic cone
of a phenyl group but that configurations which can lead
to up-field shifts for the COCHa protons without also
appreciably influencing the chemical shifts of the =CH-
protons are unlikely. (2) The up-field shifts for the
Si-CHs protons of both gis- and trans-(CH3)3Si(acac)

in benzene solution show that these protons experience
the diamagneticanisotropy of the benzene ring to a greater

extent than the internal TMS reference. Apparently, a

-25-

stereospecific solvent-solute association results from
the interaction of the r electrons on benzene and the
siloxy group. Similar stereospecific interactions between
benzene and a variety of other types of solute molecules
are well known". Such an interaction should be expected
to lead to up-field shifts for the =CCH3 protons and to
down-field shifts~for the COCHa and =CH- protons, which
is indeed the result observed for the trans isomer.

(3) For (CH3)3Si(acac) in dichloromethane solution at
-40°, where the COCHa and =CCH3 resonances of the gig_
isomer are well resolved (see below), the aCCHa and COCHa
protons of the trans isomer are deshielded by 0.12 ppm
and shielded by 0r04 ppm, respectively, relative to the
analogous protons of the gig isomer. Deshielding of the
sCCHa protons in the trans isomer is expected, because

- of the paramagnetic anisotropic effect of the adjacent
COCHa group1°. Finally, it might be mentioned that for
(CH3)3Si(acac) at -u0°, the magnitude of the allylic
coupling is slightly greater in the gig isomer («'0.5 Hz)
than in the tragg'isomer (<:0.5 Hz). Under the same
conditions, the long-range coupling between the =CH-

and C0CH3 protons is smaller in the gig isomer (A’O.O Hz)
than in the 23325 isomer (~I0.5 Hz). The relative
magnitudes of the allylic coupling are in agreement with
the result normally»observed for allylic systems,‘vig.,
that cisoid coupling is slightly larger than transoid

couplingl’. The coupling constants alone, however, would

-26-

not constitute a reliable basis for the chemical shift
assignments, because no'relationship exists between allylic
coupling constants and the stereochemistry of related
a,s-unsaturated estersa°.

Several unsuccessful attempts to separate the gig_
and'ggagg isomers of (CHg)asi(acac) by gas chromatography
(cf., Experimental Section) or by vacuum distillation at
68° through a spinning band column suggest that equilibrium
is established readily between the two isomers. Facile
isomerization is further supported by the fact that a
freshly distilled sample contained the same ratio of
isomers as a sample that had aged 6 months at room tem-
perature. The aged sample must surely be at equilibrium,
because the gig methyl enol ether of acetylacetone is
converted to "pure" trans isomer within 8 days at ambient
temperature’. Thus, solutions of the triorganosilicon
acetylacetonates in chlorobenzene were assumed to be
at equilibrium after one week at room temperature, and
the gi§_to trans ratios, shown in Table V, were determined
by planimetric integration of =CH- nmr lines. With the
exception of the phenylsilyl derivatives, the equilibrium
amount of £;§,isomer increases with increasing electron
withdrawing ability of the substituents on silicon.

This relationship between the gi§.to trans ratios and the
polarity of the silicon substituents suggests that a long-
range electrostatic interaction may exist between silicon

and the dangling carbonyl oxygen atom in the cis isomers.

-27-

Table V

Equilibrium Ratio of Cis and Trans Enol Ether

Isomers for Triorganosilicon Acetylacetonatesé

 

 

Compound [ElEJ/ngggg]
(ng4Hg)(CHa)2Si(acac) 0.289 i 0.029
(C2Hs)(CHs)2Si(acac) 0.29 t 0.02
(CH3)3Si(acac) 0.3u i 0.0a
(CF3CH20H2)(CH3)2§1(acac) '0.59 t 0.05
(CH2=CH)(CH3)2Si(acac) 0.38 t 0.02
(CgH3)(CH3)2Si(acac) 0.51 t 0.02
(c.H5)2(0H3)Si(acac) 0.25 i 0.02

 

‘g In chlorobenzene solution at room temperature; con-
centration is 0.60 m, ‘b All values are averages of five
spectral copies. ‘9 Errors are estimated at the 95%

confidence level.

Such an interaction would also account, in part, for the
enhanced stability or these gigrtriorganosilicon acetyl-
acetonates relative to the gig form of the methyl enol
ether of acetylacetone. The gig to giggg ratios for
(CaH5)(CH3)2Si(acac) and, especially, (c.H5)2(0H3)Si(acac)
are lower than expected on the basis of inductive effects,
but steric factors could weaken the long-range silicon-
cxygen interaction in the gig isomers of these derivatives.

The nmr data for the trimethylsilyl derivatives of
hexafluoroacetylacetone and dipivaloylmethane suggest
that these compounds exiSt almost exclusively as the
giggg and gig.isomers, respectively. A 10% solution of
(CH3)3Si(hfac) in carbon tetrachloride exhibits a
single (CH3)3Si resonance {-21.2 Hz) and a single -CH=
resonance (~378.3 Hz). The F19 -nmr spectrum of this
compound showed two sharp lines of equal intensity which
were assigned to the two nonequivalent CFa groups in
the giggg isomer. In neither the proton or fluorine nmr
spectrum was there evidence for the presence of the gig
isomer. The chemical shift difference between the fluorine
lines was pr0portional to the magnetic field strength
(442.5 Hz at 100 MHz and 260.0 Hz at 56.n MHz), which
indicates that the two lines are indeed singlets and not
an anomalous doublet.

The nmr spectrum of (CH3)ssi(dpm) (10% in carbon
tetrachloride) showed single (CH3)3Si, -CH= and‘g-Cxfla
resonances at -2l.2, -65.3 and —378.3 Hz, reapectively.

  

run-“um 'leflnnl'um ‘

-29-

The existence of one g-C4H9 line is attributed to the
presence of only the gig isomer which is undergoing a
rapid stereochemical rearrangement process similar to that
described above for the gig7R33i(acac) compounds. A
single, sharp g-C4Ha line was also observed in a CH2C12-
C32 solution at -95°. Apparently, the rearrangement is

so facile that the nonequivalent £fC4H9 groups cannot be
observed on the nmr time scale even at extremely low
temperature. The.possibility of a stable penta-coordinated
silicon species was ruled out by the fact that an un-
coordinated C=0 stretching vibration is observed in the
infrared spectrum (cf., Section III 0).

The existence of pure isomers for (CH3)3$i(hfac) and
(CH3)3Si(dpm) is explained, in part, by the long-range
interaction between silicon and the dangling oxygen atom
proposed above to account for the variation of gig,to
giggg,ratio of isomers for the Rasi(acac) compounds. In
(CH3)3Si(hfac), the electron withdrawing effect of the
CF3 group apparently decreases the effective negative
charge on the uncoordinated oxygen atom and this decrease
in charge leads to destabilization of the gig_conformation.
0n the other hand, the inductive effect of the gyc.H.
group in (CH3)3Si(dpm) should enhance the stability of
the gig.conformation.

E. ‘39; Line Broadening3Studies
Gutowsky and Holm21 have shown that the mean life-

times, TA and TB, of protons exchanging between two

-30-

nonequivalent sites can be determined from the nmr line
shapes of 8v, the frequency separation between the res-
onance components in absence of exchange, and T2, the
transverse relaxation time, are known. The mean life-
times are related to the quantity T by; = TATE/TA + T3.
Since the two nonequivalent sites in the systems con-
sidered here are equally populated, TA = TB = 2T. In
the region of slow exchange 5v for the RSSi(acac) com-
pounds is temperature dependent, presumably, because

of temperature-dependent solvation effects. Since the
line widths of both the uncoupled cocne resonance in
the region of slow exchange and the time-averaged
resonance in the region of fast exchange vary with tem-
perature, T2 is alSo temperature dependent. The tem-
perature depencence for 8v and T2 is analogous to the
behavior found previously for the non-equivalent methyl

22’23. values

protons in chelated metal acetylacetonates
of'Ju in the region of exchange were obtained by linear
extrapolation of data in the region of slow exchange.
Values of T2 in the region of exchange were obtained
from the extrapolated values of the line widths for
(CH3)3Si(acac), as determined by J. J. Howe1°. The
relaxation times of the =CCH3 protons below coalescense,
where they are slightly coupled to the =CH- proton, were

assumed to be equal to the relaxation times found for

the cocne protons.

-31-

Values of T in the region of exchange below the coal-
escense temperature were determined by comparing the
observed width at half maximum amplitude of the uncoupled
COCHa resonance with the width calculated from the Gutowsky-
Holm equation for various trial values of '1‘. Although the
small coupling between the -CH= and =CCH3 protons below
coalescense was not included in the calculated spectra,
the error generated in the computed values of T is
estimated to be only approximately 2%. Above the coal-
escense temperature 'I‘ was determined by comparing the
observed and computed widths of the time-averaged
resonance line.

Using a method similar to those described above, Howe
has determined that the following activation parameters

for the exchange of methyl groups in cis-(CH3)3Si(acac)
13.8 t 0.5 kcal/mole, A = exp-

:in chlorobenzene: Ea
+
(13.05 i” 0.54), [332:0

The first order rate constant, k, is related to the

0.8 t 2.5, and has, = 851 sec’l.

quantity ’1‘ by k = ('2T)“. First order rate constants for
methyl group exchange in the Rasi(acac) complexes pre-
pared in this study were determined at selected temperatures
in the region of exchange. The exchanged broadened methyl
prot on resonances for each compound at each selected
temperature are illustrated in Figure l. The nmr line
Shape parameters are collected in Table VI. The un-
certainty in the value of by for gig - (CFSCH2CH2)(CH3)2

SMacao) is estimated to be g_a_. i‘ 2.0 Hz; for the other

Iriqgure 1.

-32-

Exchange-broaden acetylaceonate methyl proton
resonances for cis-triorganosilicon acetyl-
acetonates in chlorobenzene. Dashed lines are

the acetylacetonate methyl resonaces of the

trans isomer in each equilibrium mixture.

Total concentration is 0.60.3.

-33..

 

---\

tannin-nu H

"'

I

(C2H5)(CH3)2SI(acac), -23.3°

Inna-Um: o I opal-icon

\
'-‘- ......

Imam-nun 'IIWHJVII

/

I

’

\

 

(CH2=CH)(CH3)aSi(acac), 0.7°

up---

 

_

"’

/

(C3H5)(CH3)2Si(acac), -l2.7°

 

(CF3CH2CH2)(CH3)2Si(acac), -12.7°

 

/ ./

mas.---

, a. v

I\\ I\\ -8
.wn ”NH-um} Mun-um- umuUn

   

(C5H5)2(CH3)Si(acac), “12.70

\

‘-'

-34-

Table VI

Nmr Line Shape Parameters for the Acetylacetonate methyl

Resonances of Cis-Triorganosilicon Acetylacetonates-9‘-

 

 

Compound [Temp., Line Width-9, 6v, Hz
°c Hz
(_:_:_-c.n.)(cne)2Si(acac) -25.0 2.513% 0.058 156.769
(C2H5)(CH3)2Si(acac) -25.0 2.71 i' 0.05 56.86
(CH2=CH)(CH3)2Si(acac) 0.7 5.54 t 0.04 29.92
(c.H5)(CHe)2Si(aca'c‘-) -12.7 >10.0 41.40

(CF3CH2CH2)(CH3)2Si(acac) -12.7 1.81 i 0.02 20.40

(CQH5)2(CH3)Si(acac) -l2.7 5.44 t 0.04 52.78
_a_ In chlorobenzene solution; concentration is 0.60 m.

1;; Line widths for '(g-c.H.)Si(acac) and (C2H5)(CH3)2-
31(acac) refer to the COCHa resonance component below
the coalescense temperature; all others are for the
1Slime-averaged resonance above coalescence. g Average
or at least three spectral copies. g Errors are for one
s1Jandard deviation. _e_ All values of 5v were obtained by

linear extrapolatidn of the temperature dependence of

5V in the region of slow exchange.

-35-

cis isomers, the uncertainty in 6v is believed to be
t 1.0 Hz or less.

It should be noted that for several of the gig_
derivatives, the temperatures at which accurate line
widths could be determined was limited by the acetyl-
acetonate methyl resonance of the giggg isomers present
in the equilibrium mixtures (gi,, Figure 1). In the
case of (C3H5)(CHg)aSi(acac), for example, the time-
averaged methyl resonanCe of the gig’isomer at -12.7°
is so broad that it is barely detectable above the base
line. Above -l2.7° the time-averaged line is superimposed
on =CCH3 resonance of the‘ggggg isomer, and in the region
of exchange below coalescence, the COCHa resonances of the
two isomers are nearly superimposed. Therefore, only an
upper or lower limit could be determined for the rate
constant at ~12.7°. The lower limit was estimated from
the simplified Gutowsky-Helm equation (cf., equation 6
in ref. 21) and the upper limit was established by
assuming the width of the time averaged resonance to
be > 10 Hz.

values of the first-order constants are shown in
Table VII, along with calculated values of the Arrhenius
activation energies. The errors in the rate constants for
gig-(n-cm.)(cna)251(acac) and gig-(C2H5)(CHa)aSi(acac)
are based on the uncertainties in the observed line width

0f the COCHa resonance; the estimated error in.&z(I 1.0 Hz)

-36-

Table VII

Kinetic Data for Acetylacetonate Methyl Group Exchange

in Cis-Triorganosilicon Acetylacetonates-

a

 

 

Compound Temp., k, s‘ec-1 Ea.
°C kcal/mol

(arc-Ha)(CHs)2si(acac) -25.3 5.35-i 0.169 14.1
(CgH5)(CH3)2Si(acac) -25.5 5.96 I 0.10 14.0
(CH2=CH)(CH3)2Si(acac) 0.7 500 I 50 15.0
(c.H5)(CHs)2Si(acac) -12.7 >91.9- <500 <15.2,
:>l2.6

(CF3CH2CH2)(CH3)2Si(acac) -12.7 621 I 118 12.2
(CeHs)2(CH3)Si(acac) -12.7 628 i 58 12.2

g In chlorobenzene solution; total concentration of

(CH3)381(acac) is 0.60 g.

1:; Basis for estimates of

error are described in the text.

_37 .—

propagates a very small error ((0.05%) in the rate constant.
0n the other hand, errors in the rate constants for the
other gig isomers, which were determined from the widths
of the time-averages lines above coalescence, are due
‘mainly to uncertainties in 8v. For example, the error
generated in the rate constant for gig-(CH2=CH)(CH3)2-
Si(acac) due to the uncertainty in the line width is only
1.0%, whereas the error propagated by an uncertainty of

i 1.0 Hz in SV is 6.0%. The activation energies shown in
Table VII were calculated from the first-order rate
constants by assuming that the frequency factor is equal
to the value obtained for gig-(CH3)3Si(acac).

From the data in Table VII it may be concluded that
there is a general increase in the rate of acetylacetonate
methyl group exchange with increasing polarity of the
substituents on silicon. For the gig-R(CH3)aSi(acac)
compounds, the rate increases in the order R =‘g:C4H.‘<
C2H5 < CH3 < CH2=CH, CaHs < CF30H2CH2, and the lability
of gig- (C5H5)2(CH3)Si(acac) is comparable to that of
(CF3CH2CH2)(CH3)2Si(acac). The dependence of the rates
on the polarity of the silicon substituents is consistent
'with a mechanism involving formation of a five-coordinated
silicon intermediate or transition state. Although
several factors contribute to the energy required for such
a bonddmaking activation process, as the electron-
withdrawing ability of the substituents is increased, the

resulting increase in positive charge on silicon should

 

-38-

faoilitate the use of a metal d-orbital in achieving the
transition state28. Relative to the alkyl-substituted
silicon derivatives, the phenylsilyl derivatives are less
labile than might be expected on the basis of 0 inductive
effects alone. However, the phenyl group has a greater
steric requirement than the other substituents studied
and. also, probably participates in ligand e>metal v
bonding. Both 01 these latter factors would tend to lower
the rearrangement rate. Since gig:(CgH5)2(CH3)Si(acac)

is more labile than gig-(C3H5)(CH3)2Si(acac), however,

a inductive effects must play an important role in
determining the relative labilities of these derivatives.
A Hammett-Taft reaction constant (p*) of 1.67 at

25° was estimated‘for the rearrangement of the gig-
R(CH3)2Si(acac) derivatives in which R is an alkyl group.
The Taft substituent constants and extrapolated values

of the first order rate constants are give in Table VIII.
The plot of log k/ko Kg. 0* is shown in Figure 2. It

is noteworthy that the value of 0* for CF30H20H2 has been
recently found to be solvent dependent, ranging from 0.32
in water to gg, 1.0 in nonpolar solvents such as hexane.
Based on the plot shown in Figure 2, it might be expected
that the value ofcr* for CF3CH2CH2 in chlorobenzene

solution is gg, 0.73.

 

-39..

Table VIII

Taft Parameters for Methyl Group Exchange in cis-R(CH Si(acac) Derivatives in

3)2

Chlorobenzene Solution

 

 

R 0*1 kzseh' log k/ko
n-can9 -0.130 513 -o.2oo
0235 -n.100 605 -0.143
CH3 0.00 851(k.) 0.00
CH2 - cu . 0.362 3,275 0.582
cracuzcu2 0.32—1.001 15,050 1.25

 

 

_g All values of 0* were taken from ref. 24 unless otherwise noted. ‘g Values
of first order rate constants were calculated from the Arrhenius activation energies

given in Table VII and a frequency factor of exp(13.052). g Ref. 25. g Ref. 26.

-40-

."‘ "O‘ . 'o.

 

Figure 2. Log k/ko 3g. 0* plot at 25° for methyl group
exchange in cis-R(CH3)aSi(acac) derivatives

in chlorobenzene.

-41-

1

1.2-

 

TFP

TFP

1.0'

0.8-

V1

.05- m3
.IH..wI

001‘ P

0.2-

 

6*

1C).

1]..

12?.

13.

14.

15.
l6.

17.

-42-

BIBLIOGRAPHY

w. Dilthey, Ber., L6, 925 (1905)
R. Pike and R. Luongo, ,1. Am. Chem. Soc., 81, 1405

 

(1965).
D. w. Thompson, Inorg. Chem., g, 2015 (1969).
W. H. Knoth, Ph.D. Thesis, the Pennsylvania State 1...

University, University Park, Pennsylvania, 1954. 1
R. West, _J;._Am. Chem. Soc., _8__Q, 3246 (1958).

L. H. Sommer, “Stereochemistry, Mechanism and
Silicon" McGraw Hill Inc., N.Y., N.Y., 1965, p. 14.

 

B. Eistert, F. Arndt, and L. Loewe, Chem. Ber., 84, g
156 (1951); EA; 3:. 7525: (1951).

R. West, J. Am. Chem. Soc., 89, 5246 (1958).
J. J. Howe and T. J. Pinnavaia, J. Am. Chem. 300.,
21. 5578 (1969). """"“"“""

J. J. Howe, PersonaL,Communication, Michigan State
University, 1969.-

A. L. Van Geet, Anal. Chem., i4, 2227 (1968); Paper
presented at the 10th Experimental NMR Conference,
Mellon Institute,- Pittsburgh, Penn., February, 1969.

G.T. Benke and K. Nakamoto, Inor . Chem., 6, 440
(1967 - K. Nakamoto and A. E.‘ Ma—B—Tfrte , J. chem. Phys“
2, 5 8 (1960).

M. L. Morris, R. W. Moshier and R. E. Sievers inorg.
Chem., _2_, 411 (1965).. ’

‘ G. Podolsky, private communication, Michigan State

University, 1969.
R. Menke and E, Funk, 2. Electrochem., 99, 1124 (1956).

an. Anteunis and N. Schamp, Bull. Soc. Chim. Belges,
E.- 330 (1967) .

J. W. Ensley, J. Feeney and L. H. Sutc. Liffe, High
Resolution Nuclear Magnetic Resonance Spectroscopy",

gel. 2, Pergaman Press, New York, N.Y., 1966, pp. 841-

18.

19.
2CL

221.

2H2.

2E5.
2N4.

225.

2&5.

-43-

L. M. Jackman and R. H. Wiley, J. Chem. Soc., 2886
(1960).

s. Sternhell, Rev. Pure Appl. Chem., i5, 15 (1964).

R. R. Fraser and D. E. McGreer, Can. J. Chem., 32,
505 (1961).

H. S. Gutowsky and C. H. Holm J. Chem. Phyg. g5
1228 (1956). ’ ’ ’

T. J. Pinnavaia, J. M. Sebesan, II, and D. A. Case,
iporg. Chem., 8, 644 (1969).

R. 0. Fay and R. N. Lowry, ibid., g, 1512 (1967).

R. W. Taft, Jr., in “Steric Effects in Organic
Chemistry", M. S. Newman, Ed., John Wiley and Sons,
Inc., New York) N.Y., 1956, p. 591.

M. M. Kreevoy and R. W. Taft, Jr., J. Amer. Chem.
Soc., 19, 4016 (1957).

J. Lipowitz, Dow Corning Corporation, Personal
communication, 1970.

-44-

APPENDIX A

Mass Spectra

r.asmla~xnmuhwiii”\if¢u AAA- . .

HARE:

EHPIRICAL FORMULA: SlCllHZZOZ

-45-

NDRHALIIED MASS SPECTRUM

INSTRUMENT: HS-lZ
AtCEL veil:

BASS
33.0
34.0
35.0
36.0
37.0
38.0
39.0
40.0
41.0
42.0
43.0
44.0
45.0
46.0
47.0
48.0
49.0
50.0
51.0
52.0
53.0
54.0
55.0
56.0
57.0
58.0
59.0
60.0
61.0
62.0
63.0
64.0
65.0
66.0
67.0
68.0
69.0
70.0
71.0
72.0
73.0
74.0
75.0
76.0
77.0
78.0
79.0
80.0

181
0.05
0.05
0.02
0.14
0.65
1.22
6.35
1.35
0.05
1.59
55.56
3.10
6.35
0.46
3.17
0.22
0.38
0.67
0.90
0.48
1.30
0.43
1.83
1.57
1.44
3.17
36.51
3.17
7.94
0.70
1.48
0.59
1.51
2.57
1.21
0.21
1.21
0.35
3.17
1.59
14.29
2.08
26.98
2.14
7.94
1.13
1.59
0.35

8 RV

MASS
81.0
82.0
83.0
84.0

“85.0

86.0
87.0
88.0
89.0
90.0
91.0
92.0
93.0
94.0
95.0
96.0
97.0
98.0
99.0
100.0
101.0
102.0
103.0
104.0
105.0
106.0
107.0
108.0
109.0
110.0
111.0
112.0
113.0
114.0
115.0
116.0
117.0
118.0
119.0
120.0
121.0
122.0
123.0
124.0
125.0
126.0
127.0
128.0

souace TEMP:
TRAP cuaurz_1oo MIC AMPS

LEI
IJOZ
0.48
0.90
0.46
14.29
1.78
2.21
0.27
0.46
0.06
0.56
0.24
12.70
1.11
0.03
0.38
1.05
0.51
3.17
6.35
3.08
0.44
1.62
0.19
1.87
0.38
0.65
0.10
0.27
0J02
0.43
0.33
1.97
1.48
11.11
1.71
3.17
0.54
4.76
0.94
1.46
0.38
0.56
2.38
1.27
0.05
4.76
0.87

HASS
129.0

130.0

131.0
132.0

"133.0

134.0
135.0

‘136.0

137.0
138.0

'139.0
140.0
141.0
142.0
143.0
144.0
145.0
146.0
147.0
148.0
149.0
150.0
151.0
152.0
153.0
154.0
155.0
156.0
157.0
158.0
159.0
160.0
161.0
162.0
163.0
164.0
165.0
166.0
167.0
168.0
169.0
170.0
171.0
172.0
173.0
174.0
175.0
176.0

2-(BUTYLDIHETHYLSILOXY)-4-KETOPENTENE-2

170

181
0.71
0.22
1.21
0.48
28.57
3.17
3.17
0.44
0.78
0.10
1.08
0.22
1.73
1.29
15.87
2.06
1.56
0.21
0.30
0.02
0.21
0.48
0.16
0.25
0.17
0.13
0.44
1.70
100.00
11.11
3.17
0.48
0.10
0.02
0.02
0.02
0.27
0.02
0.10
0.06
0.68
0.16
0.30
0.06
0.19
0.02
2.56
0.41

MASS
177.0
178.0
179.0
180.0
181.0
182.0
183.0
184.0
185.0
186.0
187.0
188.0
189.0
190.0
191.0
192.0
193.0
194.0
195.0
196.0
197.0
198.0
199.0
200.0
201.0
202.0
203.0
204.0
205.0
206.0
207.0
208.0
209.0

INLEI TEMP:
IONIZING PDT: 80

181
0.19
0.02
0.10
0.08
0.30
0.03
0.13
0.02
0.63
0.19
0.06
0.02
9.52
2.00
0.86
0.08
0.24
0.02
0.27
0.22
4.76
1.30
26.98
3.17
1.37
0.10
0.05
0.02
0.03
0.02
0.14
0.02
0.02

214.1383

135

BASS

181

 

NAME:

EMPIRICAL FORMULA:

-15-

NORMALIIED MASS SPECTRUM

INSTRUMENT:
ACCEL VOLT:
BASS 181
14.0 2.63
15.0 5.79
16.0 0.53
17.0 0.02
18.0 11.58
19.0 0.02
20.0 0.07
22.0 0.01
24.0 0.09
25.0 0.34
26.0 1.58
27.0 5.26
28.0 70.53
29.0 2.11
30.0 0.23
31.0 2.63
32.0 12.63
33.0 0.11
34.0 0.05
36.0 0.10
37.0 0.42
38.0 1.03
39.0 5.79
40.0 0.53
41.0 1.58
42.0 2.11
43.0 45.79
44.0 2.11
45.0 12.63
46.0 0.82
47.0 5.26
48.0 0.32
49.0 0.39
50.0 0.47
51.0 0.62
52.0 0.30
53.0 1.05
54.0 0.38
55.0 1.05
56.0 0.68
58.0 5.26
59.0 43.68
60.0 3.68
61.0 12.63
62.0 0.53
64.0 2.63
65.0 0.85
66.0 0.45

MS-12

8655
67.0
68.0
69.0
70.0
71.0
72.0
73.0
74.0
75.0
76.0
77.0
78.0
79.0
80.0
81.0
82.0
83.0
84.0
85.0
86.0
87.0
88.0
89.0
90.0
91.0
92.0
93.0
94.0
95.0
96.0
97.0
98.0
99.0
100.0
101.0
102.0
103.0
104.0
105.0
106.0
107.0
108.0
109.0
110.0
111.0
112.0
114.0
115.0

S|C9H1802

SOURCE TEMP:
TRAP CURNT:

181
1.19
0.24
1.18
0.36
3.16
0.75
1.58
1.58
30.53
2.11
7.89
0.53
1.05
0.14
0.45
0.42
0.87
0.41
8.42
1.05
38.42
3.16
4.21
0.35
0.64
0.08
2.63
0.27
1.05
0.14
1.05
0.45
5.26
1.58
2.11
0.27
0.34
0.12
0.22
0.08
0.53
0.05
0.26
0.07
0.61
0.27
0.94
6.32

HASS
116.0
118.0
119.0
120.0
121.0
122.0
123.0
124.0
127.0
128.0
130.0
131.0
132.0
133.0
134.0
135.0
137.0
138.0
139.0
140.0
141.0
142.0
143.0
144.0
145.0
147.0
148.0
149.0
151.0
152.0
153.0
154.0
155.0
157.0
158.0
159.0
160.0
161.0
162.0
163.0
165.0
168.0
169.0
170.0
171.0
172.0
173.0
174.0

2-1DIMETHYLETHYLSILOXY1-4-KETOPENTENE-2

170

100 MIC

181
1.02
0.12
0.41
0.05
0.07
0.21
0.34
0.13
5.79
0.83
0.20
0.31
0.07
0.53
0.18
0.24
0.13
0.04
1.05
0.23
1.05
1.18
2.63
0.46
0.21
0.24
0.03
0.06
0.10
0.03
0.42
0.07
0.26
100.00
12.63
3.68
0.34
1.11
0.17
0.09
0.04
0.55
0.61
0.55
51.05
6.84
2.11
0.19

AMPS

MASS
175.0
185.0
186.0
187.0
188.0
189.0

INLET YEHP:

186.1071

135

IONIZING PDT: 80

181

0.15
0.07
0.92
0.16
0.04
0.05

BASS

181

 

NAME:

-87-

NURMALIZED MASS SPECTRUM

EMPIRICAL FORMULA: SIC8H16OZ

INSTRUMENT:
ACCEL VOLT:
BASS 181
33.0 0.16
34.0 0.55
36.0 0.26
37.0 1.10
38.0 2.26
39.0 6.45
40.0 6.45
41.0 5.29
42.0 6.29
43.0 74.19
44.0 6.45
45.0 16.13
46.0 1.32
47.0 6.45
48.0 0.68
49.0 2.16
50.0 1.06
51.0 1.35
52.0 0.61
53.0 1.97
54.0 0.48
55.0 3.16
56.0 0.68
57.0 2.06
58.0 2.26
59.0 4.77
60.0 1.45
61.0 5.29
62.0 1.00
63.0 1.55
64.0 0.32
65.0 1.35
66.0 1.03
67.0 1.23
68.0 0.29
69.0 1.71
70.0 0.61
70.5 0.10
71.0 3.10
71.5 0.19
72.0 3.13
73.0 96.77
74-0 6.45
75-0 35.48
76.0 2.71
77.0 9.68
78.0 1.16
78.5 0.10

MS-IZ
8 RV

1
1
1
1
1
1
1
1
1
1
1
1
1
1
1
1
1
1
1
1
1
1
1
1
1
1
1

86.0
87.0

90.0

94.0
95.0
96.0
97.0
98.0
99.0
00.0
01.0
02.0
03.0
05.0
08.0
09.0
10.0
11.0
12.0
13.0
14.0
15.0
16.0
17.0
18.0
19.0
23.0
25.0
26.0
27.0
28.0
29.0
30.0
31.0
32.0
33.0

2-1TR[METHYLSILOXY1-4-KETOPENTENE

SOURCE TEMP: 115
TRAP CURNT:

181

0.81
0.19
0.35
0.32
0.68
0.52
9.68
0.77
1.19
0.13
0.32
0.16
1.68
1:42
4.71
0.35
1.68
0.16
0.90
0.39
4.77
5.00
1.74
0.23
0.35
0.19
0.26
0.10
0.13
0.39
0.16
1.45
0.35
6.45
0.90
1.61
0.13
0.16
0.23
0.23
o. “S
2.97
0.45
0.39
0.42
0.71
0.10
0.35

BASS
137.0
139.0
140.0
141.0
142.0
143.0
144.0
147.0
148.0
149.0
155.0
156.0
157.0
158.0
159.0
160.0
172.0
173.0
174.0

100 MIC AMPS

181
0.19
1.74
0.23
1.42
0.32
0.35
0.10
6.45
1.52
0.87
0.26
0.58
100.00
9.68
4.48
0.29
6.45
1.35
0.42

BASS

INLET TEMP:
IONIZING POT: 80

181

172.0915

138

BASS

181

NORMALIZED MASS SPECTRUM

-48-

184.0915

 

NAME: 2-1VINYLGTMETHYLSTLOXY7-4-KETOPENTENE-2uh“7

EMPIRICAL FORMULA: SIC9H1602

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

3....-..__..--—————u...-... .-—--. ,1". __ .-._ . .._. .

INSTRUMENT: "5'12 SOURCE TEMP: 160 INLET TEMP: 135
ACCEL VOLT: 8 KV TRAP CURNT: 100 "1C AMPS &__"10NI7TNG POT1_8O
8855 18.1 8855 181 8855 1M 8.855 181 8855 181
37.0 1.05 86.0 6.67 156.0 3.33___ _ ‘__ _w _ 7*_
38.0 1.67 87.0 25.83 157.0 32.50
39.9 12.50 88.0 1.67 158.0 4.17
40.0“ 2.sq_ 89.0 1.67 159.0 1.67 _ ‘__._ -
41.0 5.00 91.0 1.67 165.0 1.19
42.0 5.83 92.0 0.52 167.0 0.71
_ 43.0 100.00 93.0 1.67 #168.QA 0.47 __
64.9 3.33 95.0 1.67 169.0 76.67
45.0 23.33 97.0 0.02 170.0 10.00
__._ 46.0 L58 9819” 0.74 J71.L 8.33 2 _.
47.0 7.50 99.0 8.33 172.0 1.21
48.0 0.50 100.0 0.08 173.0 0.47
49.0 0.69 101.0 2.50 183.0 1.12 ~__ _
50.0 1.09 102.0 1.16 184.0 1.67
51.0 1.33 103.0 1.13
__ 52.0 0.83 105.0 2.50 ‘ __ A
53.9 3.33 107.0 1.09
54.0 0.77 199.0 1.71
55.1 5.10 110.9 0.53 w _.__ __
56.0 1.00 111.0 0.03
57.9 2.50 112.0 0.73
,__ 58.0 5.90 113.0 7.50 ___ .__.__3 _
59.0 70.00 114.0 0.77
60.0 5.00 115.0 4.17
_ 6130 25.83 116.0fl_ 0.48 _____ _fi._ A 2.2
62.0 1.67 117.0 5.83
63.0 2.50 118.0 0.80
m 64.0 4.17 _ 119.0 1.14 .___u __v ._ 3
65.0 1.67 120.0 0.49
66.0 1.11 123.0 1.60
_ 67.0 2.50 125.0 4.17 _____ _. _, 1
68.0 0.67 126.0 1.37
69.0 3.33 127.0 9.17
70.0 1.08 128.0 1.24 _fl _ _
71.0 3.33 129.0 1.88
72.0 1.82 131.0 0.62
2 "__h1339“..§:l?.uh 133.0". 1.37 , ‘_~, --
74.9 1.24 135.0 0.58
75.0 40.83 139.0 5.83
76.0 3.33 140.0” 1.30 w _2_ _
77.0 20.00 141.0 87.50
78.0 1.67 147.0 12.50
_' «19.0 1.67 143.0 5.83 “*7 _ _
81.0 0.77 144.0 0.93
82.0 0.74 145.0 0.76
__t 83.9 3.33 151.0 3333 _~_‘ __
84.0 1.67 152.0 0.59
85.0 94.17 153.0 0.89

 

NORMALTZED

-89-

MASS SPECTRUM

 

NAME: Z—lTRIFLUOROPROPYLOIHETHYLSIL0X77‘4-KETDPFNTFNEFZ

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

EMPIRICAL FORMULA: SlClOHlTnZ :3 .. _fl
INSTRUMENT: HS-IZ SOURCE TEMP: 160 INLET TEMP:
ACCFL VOLT: 8 KV TRAP CURNT: 100 MIC AMPS
BASS IHI BASS 181 HASS 181 BEES 151
33.0 2.17 83.0 1.96 132.0 0.14 185._0_ 2.23
34.0 0.08 84.0 0.66 133.0 0.02 186.0 0.03
36.0 0.24 85.0 93.48 134.0 0.46 187.0 0.07
37.0 0.64 86.0 3.76 135.0 1.23 219.0 2.17
38.0 1.65 87.0 2.09 136.0 0.15 220.0 0.42
39.3 19.57 88.0 0.22 137.0 0.02 721.0 0.15
41.0 0.03 89.0 0.88 138.0 0.39 223.9. QgLi-
42.0 0.02 90.0 0.26 139.0 1.50 224.0 0.03
43.3 100.08 91.0 0.78 140.0 0.22 225.9 0.11
44.0 3.26 92.0 0.13 141.0 1.48 235.0 0.93
45.0 8.70 93.0 2.21 142.0 0.48 236.0 0.42
46.0 0.62 94.0 0.20 143.0 0.26 237.0 0.13
47.0 9.78 95.0 2.00 144.0 0.28 238.0 ._Q.l7
48.0 0.74 96.0 0.67 145.0 0.50 239.0 13.04
49.0 5.43 97.0 1.13 146.0 0.11 240.0 2.25
50.0 1.18 98.0 0.73 147.0 0.16 24l.0__“0.67
51.0 2.17 99.0 3.26 148.0 0.02 242.0 0.04
52.0 9.65 100.0 0.01 149.0 0.05 254.0 4.35
53.0 2.17 102.0 0.25 150.0 0.02 255.0--WD.82,
54.0 0.82 103.0 1.26 151.0 3.26 256.0 n.25
55.0 0.02 104.0 0.16 152.0 0.70
56.0 0.59 105.0 1.60 153.0 0.57 __ __
57.0 2.17 106.0 0.16 154.0 0.26
58.0 4.35 107.0 0.29 155.0 1.72
%__A 59.0 75.00 108.0 0.10 156.0 0.84 _ H.
60.0 2.17 109.0 0.84 157.0 65.22
61.0 2.17 110.0 0.12 158.0 7.61
_______ 62.0 1.38 111.0 0.57 159.0 0.02
63.0 0.03 112.0 0.23 160.0 0.86
64.0 0.96 113.0 1.11 161.0 14.13
——__.______65.0 1.41 114.0 0.50 162.0 2.07 _ __
66.0 0.51 115.0 0.03 163.0 0.71
67.0 1.76 116.0 0.52 164.C 0.04
“\6800 0038L 11700 3.032 165.“ 0.78 -
69.0 2.17 118.0 0.25 166.0 0.08
70.0 0.35 119.0 0.87 167.0 0.05
—-——__ '71.0 3.26 120.0 0.13 169.0 0.39 _
72.0 1.04 121.0 0.59 170.0 0.00
73.0 2.17 127.0 0.C7 171.0 0.13
-~~—-- 74.0 .1.02 123.0 0.43 . 172.0 0.0g___u ‘
75.0 23.91 124.0 0.07 173.0 0.27
76.0 2.17 125.0 0.74 174.0 0.03
NA 59.78 126.0 0.43 175.0 0.18_____- _ __ _1
78.0 9.78 127.0 0.03 176.0 0.03
79.0 10.87 128.0 0.53 177.0 0.48
~\\80.o 0.88 129.0 0.89 178.0 0.9:___ _ H_
81.0 7.61 130.0 0.09 179.0 0.07
82.0 1.15 131.0 0.66 181.0 0.04

\u

 

754.0945

135

IQN1;jng_2073 80

MASS

131

-50-

NDPMALIZED MASS SPFCTRUM

NAME: 21°HcNVLwleTQYLSfLfix71—44k6707ENrrNr

EflPIPICAL FORMULA:

1N$TPUMEN12
flQQEL VOLT:
BASS lNI
32:9. 9096
3§.0 0.73
35.0 0.06
39-9r- 9270
37.0 1.93
3“.” 1.21
39.0 6.Q6
4“.“ 1.21
41.3 3.03
"42.1 2.47
43.9 49.70
44.0 3.n3
hۤo0n2.9-99
lob.n 1.24
47.0 1.92
_g§.0 “ 0094
49.0 1.18
50.0 2.4?
51.0 4.24
5?.” 1.21
55°” M 1-33_
55.0 1.82
56.0 0.52
57.n ‘1.82
59.0 1.21
59.0 7.4?
@9-q__fiL-13
61.0 1.21
67.0 1.30
67.1 3.03
64.0 0.97
65.n 2.47
66.0 1. 1.Rn
67.0 1.32
67.5 0.79
68.n n.35
69.5 0.61
6°.0 1.71
69.5 0.32
70.9 0.59
7”.5 0.26
71.0 _1.3?
72.0 2.50
73.0 3.02
74.“ 2.5“
75.0 9.43
76.0 1.21

MS~12
8-KVH

EASE

77.5
79.0
‘73.5
79.0
30.0
.71.0
37.0
37.6
44.0_
8%.”
86.0

237-0.

87.5
as."
‘39.0
89.5
qn,n

_90.51

91.“
9?.1‘
91.0
Q4.o
04.5

95.5
96.0

.12-0.

“295-9,

$1C13H1802

snuace Tsupz'17o
1317 ggaut: 100 MIC nnps_

131 mass
-1730... .111 .9
1.67 112.0
8.45 112.5
QJ‘Q ..“ll}-9.
1.82 114.0
0.73 115.0
1.21 - _11§.Q_
1.73 117.0
1.21 118.0
1375“ ..119°Q .
12.12 120.0
1.70 12“.5
2.27__.h121.Q.
0.99 122.0
5.53 123.”
,‘h 2‘9- . “12171-19.
2.73 175.0
1.52 126.n
_LQ.21_ - 127.Q_
10.30 128.0
1.21 128.5
3.03. '1?Q.Q_
1.42 129.5
0.06 11“.0
1.71 ”_131.Q4
0.09 137.0
“.61 113.0
1.80. “1174.2-
n.21 135.0
0.82 135.5
3.03"_fi_136.0_
7.27 136.5
n.12 137.0
3.097 377.0
0.09 130.0
6.67 140.0
7.71 141.0
1.21 147.0
n.11 141.0
0.94 143.5
7.88 144.0
2.04 145.0
6.06 -7147.g
7.09 148.0
1.21 149.0
1.21” _.150.9
1.17 151.0
0.17 152.0

1N1

1.12
0.62
0.70

3.2n_V

0.74
2.42
1.74
1.“?
1.7n
5.45
1.71
”.14
11.87
0.87
7.96

m_0.387ww

0.70
1.45
7.47
3.64
1.42

,,g.37
0.08
0.47
2.95
0.73
1.71
2.75

48.48
1.56
6.67
0.7n

15.19
1.8?
6.24
1.74
6.67
1.71
3.54
n.11
1.79
0.79
1.11
0.76
0.62
0.17
1.17
7.064

SASS

_157.3

154.”
156.0
166.9
157.0
15a.o
150.0
160.“
161.0
167.9
1K3.0
164.n
166.0
166.r
167.0

168.9

169.”
170.0
171.0
172.“
173."
174.0
175.0
176.”
177.0
178.0
179.0
180.0
181.0
182.0
1R3.“
194.0
1RR.P
185.0
197.0
199.0
199.?
190.0
191.0
107.0
191.0
194.“
195.0
196.0
199.0
190.0
2nn.fi

131
“.77
2.37
15.76
4.85
50.19
7.89
6.“6
1.86
3.64
1.61
1.n4
7.79
1.67
0.10
0.30
0.06
“.64
2.47
1.77
7.6“
1.47
0.3%
1.97
0.94
7.77
o.aa
7.49
0.69
0.97
0.18
1.n6
0.5°
7.77
7.70
0.70
".19
n.4s
0.70
1.22
1.ns
9.00
1.n2
1.8?
0.77
7.74
0.44
3.67
7.17

?%h.1071

INLFT TFHP: 17S
10N171NG

POT: RP

MASS
7’11.P
7“?.O
201.0
7’4."
2“5.“
906.0
2A7.p
2fifl.“
7‘ZOO
213.0
714.0
21‘.0
216.0
217.0
71R.n
719.0
22".”
271.n
P22.n
223.”
725.6
226.0

0.09

5 2.. "1' ~.~fiu.*.'

. *1 u .'.7.

 

In ' 7.. I

-51-

NORMAL1ZED MASS SPECTRUM

 

"RAKE?”238E13V101PHFNVLSILdk?1—4-KéfOéEfifENF

EHPIRLQAL FORMU1A32§IQJ8HZOQZ__

--—-.————.. __ --_

 

 

EASE
177-2
178.0
179.0
180.0
181.0
182.0
183.0
184.0
185.0

-186-9

187.0
188.“
189.0
199.0
‘9100

192.9

193.3
194.3
198.0
196.0
197.0

.198o0

199.0
200.0
201.0
702.0
703.0
204-0
705.0
206.3

7 207.0

708.3
799.9

”710.0

711.0
217.0

_ 213.0

714.0
715.9
716.0
717.0
719.0
219.0
770.7
771.0
727.0
793.9

INSTRUMENT: MS-lZ SOURCF 7547: 140
A££§11!DLIL 0-5M. .hTEAR_£uBfllj_LQQ_HYC AMP<
8855 131 EASE 101 0355 131
2.1129._29o06 __3129n_.“-31 179-F 0.592
34.0 0.20 82.0 0.25 130.0 0.09
35.0 0.04 83.0 0.08 131.0 0.19
‘36.o_m 9.41 84.0 0.60 132.Q_‘HQ.02
37.0 1.29 85.0 35.79 133.0 0.47
38.0 2.35 86.0 1.73 134.0 0.05
23239 .1292.-_-§T:QN._9361 _ 13530 09?“-.-
40.0 0.02 88.0 0.07 136.0 0.11
41.0 ).06 89.0 0.46 137.0 2.11
.252-0 2.5.50.“2,290.9-2.0913.-._1383Q . 0.25
43.0 100.00 91.0 3.53 139.0 1.61
44.0 2.35 92.0 7.74 147.0 0.46
2.32-9_- 2.22““ “_53.g,1H1.29 _J4l-Q__ 1.41
46.0 0.98 94.0 0.16 142.0 1.12
47.3 1.39 95.0 0.35 143.0 0.61
-29239_.29312 _.._36o9.329301__._J4Q.Q._mD-“8
49.0 0.41 97.0 0.18 145.0 0.72
50.0 1.82 98.0 1.45 146.0 0.01
"51.1”22.35 ”2299-0 _0L49r__J4I.Q, 0.59
52.0 0.92 100.0 23.51 148.0 0.05
53.0 2.29 101.0 1.54 149.0 0.14
-54.? _Q.26- 102.02“ 2.38_.U_JSQ.Q_--0-06
55.0 1.93 103.0 0.80 151.0 0.37
56.0 0.16 104.0 0.18 152.0 1.13
“SI-0 ”-9381- 10529 _.Z-15 ___JS3.C__.0369
58.3 2.35 106.0 0.38 154.0 1.40
59.0 1.14 107.c 0.24 155.0 2.35
__2§£:1.m_231&” -.1993£-- 11F82u__12699_«_“-54
61.0 0.51 109.0 0.06 157.0 2.40
67.0 0.16 11C.0 0.01 158.0 C.11
61o°2.fi-9€2 Ell-C 9204. .J‘E-QWWC-33
64.0 0.28 112.0 0.02 160.0 0.06
65.0 1.73 113.0 0.13 151.0 0.54
- -bb-”,_”2235_. 114-0 ._Os”5_uu_192e9___P-"7
67.0 0.87 115.0 0.76 163.0 0.15
68.0 0.1? 116.0 0.19 164.C 0.07
69.0___1.4b _ -117.0 “_0-512_u_165.QH2 1.77
70.0 0.98 118.0 0.09 165.0 0.74
71.0 0.27 119.0 1.35 167.0 0.31
2.77.0.“ 2.35 120.0 _ 0.31 L168.Q 0.04
73.0 0.89 121.0 0.61 169.0 0.13
74.0 0.46 122.0 0.08 170.0 0.13
.25,3 5 1.25 ”123.0 70.71 m_171.g_ 0.07
76.0 0.45 124.0 0.04 172.0 0.09
77.0 2.35 125.0 0.07 173.0 0.05
70.0‘ ”5.01 ~__1__26.(§ 7.13 w___174.g 0.01
79.0 1.14 127.0 1.00 175.0 0.69
80.0 0.12 128.0 0.61 175.0 0.11

224.0

296.1225
1NLET 7‘8”: 1‘8
10N171NC POT: 80
181 8335 181
”.1? 225.0 0.44
9.79 726.0 “.‘5
0.78 227.0 0.18
0.89 228.0 ".‘6
2.85 729.0 9."1
0.54 230.0 0.01
P.1h 7‘1." 0.“?
9.06 232.“ 9.85
0.99 211.0 1.11
'1.01 734.0 7.11
9.02 735.0 0.19
0.”1 736.” 0.07
0.07 737.0 0.99
2.91 718.0 0.91
F.19 719.0 n.14
3.94 240.0 0.97
F.61 241.9 9.68
0.17 242.3 9.17
1.39 741.0 0.07
7.14 763.“ r‘.1f~1
4.71 264.9 9.“2
1.14 265.0 0.01
1.88 271.” 9.4?
9.32 27?.9 9.11
2.38 273.0 0.9%
9.60 275.9 0.87
0.60 776.0 0.79
".12 277.0 0.06
0.39 781.0 0.9?
0.95 282.0 0.78
“.99 281.9 9.19
0.01 791.9 0.46
(.86 292.C C.“9
9.91 293.” 9."1
0.06 P94.0 9.91
“.81 7°5.C ‘.’1
".16 796.“ 9.“
0.1%
(‘0‘:1
10“.
18.82
3.53
24.71
1.83
1.76
0.13
“07.0
9.08

-52-
NORMALIlED MASS SPECYRUH 280.0369

NAME: 1o1.1.50505-HEXAFLORO-2-781METHYLSILOXY-6-KETOPENTENE-2
EMPIRICAL FORMULA: SIC8H1002F6

 

INSTRUMENT! "5'12 SOURCE TEMP! 160 INLET TEMP: 135
ACCEL VOLT: 8 RV TRAP CURNT: 100 MIC AHPS IONIZING POT: 80 5””-
BASS 181 HA5: 181 BASS 181 BASS 181 BASS 131

33.0 0.17 82.0 0.59 130.0 0.08 196.0 0.07

36.0 0.21 83.0 0.53 131.0 0.29 195.0 0.28

36.0 0.13 86.0 0.26 132.0 0.07 196.0 2.22

37.0 0.62 85.0 2.78 133.0 0.16 197.0 0.86 g
38.0 0.66 86.0 0.27 135.0 0.66 198.0 0.18 -
39.0 2.78 87.0 2.78 136.0 0.19 199.0 0.66

60.0 3.33 88.0 0.35 137.0 0.65 200.0 1.03

61.0 1.67 89.0 1.13 138.0 0.09 201.0 1.16

62.0 2.78 90.0 0.23 139.0 1.67 202.0 0.20

63.0 17.22 91.0 13.33 160.0 0.13 203.0 0.07

66.0 5.56 92.0 0.67 161.0 0.66 207.0 0.08 E._.
65.0 13.89 93.0 5.00 162.0 0.06 208.0 0.08

66.0 1.10 96.0 0.62 163.0 0.51 209.0 0.09

67.0 11.67 95.0 1.67 166.0 0.08 210.0 0.05

68.0 0.82 96.0 0.19 165.0 2.22 211.0 13.89

69.0 10.56 97.0 0.80 166.0 0.26 212.0 1.67

50.0 1.26 98.0 0.36 167.0 3.33 213.0 0.69

51.0 1.19 99.0 0.39 168.0 0.66 216.0 0.35

52.0 0.30 100.0 1.67 169.0 1.15 215.0 8.89
53.0 9.66 101.0 0.57 150.0 0.21 216.0 1.67
56.0 0.73 102.0 0.31 151.0 0.29 217.0 1.67
55.0 2.78 103.0 2J22 152.0 0.17 218.0 0.25
56.0 1.10 106.0 0.26 153.0 0.56 219.0 0.66

57.0 1.67 105.0 0.67 156.0 0.23 220.0 0.11
58.0 1.67 106.0 0.18 155.0 0.38 221.0 0.06
59.0 1.67 107.0 0.69 156.0 0.08 225.0 0.08
60.0 0.33 108.0 0.56 157.0 1.67 231.0 0.11

61.0 0.76 109.0 0.52 158.0 0.26 232.0 0.38
62.0 1.09 110.0 0.26 159.0 0.26 233.0 0.07
63.0 10.00 111.0 0.19 163.0 0.09 236.0 0.13
66.0 0.83 112.0 0.06 166.0 0.06 261.0 0.12
65.0 1.10 113.0 0.38 165.0 0.37 266.0 0.53
66.0 0.76 116.0 0.05 166.0 0.07 267.0 0.08
67.0 1.16 115.0 1.16 167.0 0.27 250.0 0.61
68.0 0.37 116.0 0.16 169.0 11.67 251.0 0.08
69.0 58.33 117.0 0.66 170.0 0.68 261.0 0.05
70.0 2.22 118.0 0.25 171.0 0.12 263.0 0.06
71.0 1.67 119.0 11.11 172.0 0.22 265.0 81.67
72.0 6.66 120.0 0.62 179.0 0.10 266.0 11.67
76.0 6.67 122.0 0.76 181.0 0.26 268.0 0.29
75.0 28.33 123.0 0.28 182.0 0.13 271.0 0.56
76.0 2.78 126.0 0.07 183.0 0.06 272.0 0.13
77.0 100.00 125.0 0.21 186.0 0.09 273.0 0.06
78.0 6.67 126.0 0.06 185.0 0.11 275.0 0.06
79.0 3.89 127.0 1.12 186.0 0.21 278.0 0.06
80.0 0.67 128.0 0.18 192.0 0.07

81.0 8.33 129.0 0.27 193.0 0.33

NORMALIZED

-53..

MASS SPECTRUM

NAME! 2020606-7ETRAHETHYL-3-TR1NEYHYLSILOXY-S-KETOHEPTENE-3

EMPIRICAL FORMULA:

INSTRUMENT:
A0§EL VOLT:
8155 181
12.0 0.11
13.0 0.10
14.0 2.04
15.0 1.36
16.0 0.05
17.0 1.14
10.0 0.04
20.0 0.06
22.0 0.01
2‘00 0.03
25.0 0.14
26.0 0.02
27.0 1.36
20.0 65.99
29.0 6.12
30.0 0.14
31.0 0.33
32.0 10.00
34.0 0.03
36.0 0.05
37.0 0.20
30.0 0.36
39.0 3.40
40.0 0.90
41.0 11.56
42.0 1.11
43.0 0.16
44.0 0.60
45.0 6.00
46.0 0.49
47.0 1.51
40.0 0.09
49.0 0.16
50.0 0.46
51.0 0.00
52.0 0.35
53.0 1.10
54.0 0.22
55.0 1.36
56.0 1.00
57.0 26.53
50.0 1.37
59.0 1.36
60.0 0.42
61.0 0.01
62.0 0.10
63.0 0.33
64.0 0.12

HS-12

$1c14 02002

500006 TEMP: 170

TRAP CURNT: 100 MIC
BASS 1N1 8155 181.
65.0 0.67 113.0 0.75
66.0 0.50 ‘114.0 0.20
67.0 1.51 115.0 0.49
60.0 0.15 116.0 0.10
69.0 1.37 117.0 0.31
70.0 0.60 110.0 0.04
71.0 0.52 119.0 0.40
72.0 1.36 120.0 0.07
73.0 46.26 121.0 0.17
74.0 3.40 122.0 0.06
75.0 15.65 123.0 0.73
76.0 1.36 124.0 0.10
77.0 1.36 125.0 2.04
70.0 0.56 126.0 0.20
79.0 0.00 127.0 0.03
00.0 0.14 120.0 0.42
01.0 4.00 129.0 0.10
02.0 0.44 130.0 0.04
03.0 0.93 131.0 0.16
04.0 0.20 132.0 0.02
05.0 2.04 133.0 0.32
06.0 0.22 134.0 0.05
07.0 0.20 135.0 0.16
00.0 0.03 136.0 0.07
09.0 0.43 137.0 0.07
90.0 0.07 130.0 0.12
91.0 0.97 139.0 0.55
92.0 0.19 140.0: 0.15
93.0 0.39 141.0 1.36
94.0 0.07 142.0 0.52
95.0 0.54 143.0, 0.46
96.0 0.10 144.0 0.10
97.0 0.52 145.0 0.07
90.0 0.27 147.0 1.36
99.0 2.72 140.0 0.34
100.0 1.10 149.0 0.24
101.0 0.50 150.0_ 0.04
102.0 0.07 151.0 0.20
103.0 0.19 152.0 0.12
104.0 0.06 153.0 0.20
105.0 0.54 154.0 0.15
106.0 0.07 155.0 0.60
107.0 0.29 156.0 0.35
100.0 0.07 157.0 0.90
109.0 6.00 150.0 0.12
110.0 0.74 159.0 0.20
111.0 0.73 160.0 0.03
112.0 0.14 161.0 0.07

AMPS

HASi
163.0
166.0
165.0
166.0
167.0
168.0
169.0
170.0
171.0
172.0
173.0
175.0
176.0
177.0
178.0
179.0
180.0
181.0
182.0
183.0
186.0
185.0
186.0
187.0
189.0
191.0
193.0
196.0
195.0
196.0
197.0
198.0
199.0
200.0
201.0
202.0
203.0
205.0
207.0
208.0
209.0
210.0
211.0
212.0
213.0
216.0
215.0
216.0

256.

INLET TEMP! 135

[ONIZING

LEI
0.05
0.01
0.31
0.09
0.65
0.19
1.12
0.35
0.26
0.08
0.02
0.09
0.01
0.06
0.03
0.12
0.10
0.73
0.19
0.01
0.01
1.18
0.19
0.05
0.03
0.02
0.15
0.05
1.31
0.66
0.99
0.29
100.00
15.65
6.76
0.56
0.10
0.05
0.06
0.02
0.61
0.62
2.72
0.85
1.09
0.20
0.05
0.15

P01: 80

0155
217.0
218.0
219.0
220.0
221.0
222.0
223.0
226.0
225.0
226.0
227.0
228.0
230.0
232.0
233.0
236.0
236.0
238.0
239.0
260.0
261.0
262.0
263.0
266.0
255.0
256.0
257.0

1851

181
0.83
0.18
1.36
0.60
0.13
0.01
0.09
0.06
1.33
2.06
0.56
0.13
0.01
0.16
0.03
0.07
0.01
0.01
0.10
0.05
23.81
6.08
0.80
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.54-

APPENDIX B

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APPENDIX C

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