Nitrous oxide (N2O) is a potent greenhouse gas with over 310 times the warming power of CO2 and accounts for 6% of global greenhouse gas emissions.[1] The warming power and extended half life of N2O makes it a threat to the atmosphere and environment.1,2 To tackle the threat N2O poses to the atmosphere, the chemistry of N2O is being explored for applications as a substrate in oxygen atom transfer reactions due to its high thermodynamic oxidizing power (ΔGf – 104.2 kJ/mol).[2] Herein, we report the first crystallographic characterization of the pincer iridium hydride (PNP)IrH2 catalyst, PNP = [N(2-PiPr2-4-Me-C6H3)2] and the (PNP)Ir(H)Cl complex. Notably, (PNP)IrH2 can perform selective α C–H activation of linear and cyclic ethers as demonstrated with the reported isolation of the (PNP)Ir=C(C3H6O) carbene complex. The chemistry of dinitrogen is well-studied due to the significance of the nitrogen cycle and its relevance in the industrial Haber-Bosch process. By contrast, the chemistry of the heavier pnictogens is underexplored with the d- and f-block elements. Unlike lighter pnictogens, bismuth is intriguing due to significant relativistic effects that lead to interesting physical properties, like enhanced spin-orbit coupling and increased magnetic anisotropy.[3] Herein, we report the isolation of the molecular bismuth-bridged holmium lanthanide complex, (Cp*2Ho)2(μ-ƞ2:ƞ2-Bi2), where two holmium(III) centers are linked through a Bi2 2- unit. This marks the first report of a holmium–bismuth bond in a molecular compound. References: [1] Edenhofer, O., R.; Pichs-Madruga, Y.; Sokona, E.; Farahani, S.; Kadner, K.; Seyboth, A.; Adler, I.; Baum, S.; Brunner, P.; Eickemeier, B.; Kriemann, J.; Savolainen, S.; Schlömer, C.; von Stechow, T.; Zwickel and J.C. Minx, eds. Cambridge University Press: New York, NY, 2014. [2] Trogler, W. C. Coord. Chem. Rev. 1999, 187, 303-327. [3] Zhang, P.; Nabi, R.; Staab, J. K.; Chilton, N. F.; Demir, S. J. Am. Chem. Soc. 2023, 145, 9152-9163.
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