Bite-angle bending as a key for understanding group-10 metal reactivity of d(10)-[M(NHC)(2)] complexes with sterically modest NHC ligands

Florian Hering, Joern Nitsch, Ursula Paul, Andreas Steffen, F. Matthias Bickelhaupt, Udo Radius

Research output: Contribution to JournalArticleAcademicpeer-review

Abstract

Synthesis, characterization and investigations on the reactivity of the novel metal basic, yet isolable 14 VE NHC-complexes [M0(iPr2Im)2] (M = Pd 3, Pt 4; iPr2Im = 1,3-di-isopropyl-imidazolin-2-ylidene; VE = valence electron; NHC = N-heterocyclic carbene) is reported and compared to the chemistry of the corresponding nickel complex. Quantum chemical analyses reveal that differences in the reactivity of group 10 NHC complexes are caused by differences in the rigidity and thus activation strain associated with bending the corresponding d10-[M(NHC)2] fragments during reaction. These results should have implications for the understanding of the fundamental steps in catalytic cycles, in which such complex fragments are employed.
Original languageEnglish
Pages (from-to)1426-1432
Number of pages7
JournalChemical Science
Volume6
Issue number2
DOIs
Publication statusPublished - 3 Dec 2014

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