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Chemical Science

Bite-angle bending as a key for understanding group-10 metal reactivity of d10-[M(NHC)2] complexes with sterically modest NHC ligands†‡

Check for updates Florian Hering,a Jörn Nitsch,a Ursula Paul,a Andreas Steffen,a F. Matthias Bickelhaupt*bc and Udo Radius*a Author affiliations

* Corresponding authors

a Institut für Anorganische Chemie, Julius-Maximilians-Universität Würzburg, Am Hubland, D-97074 Würzburg, Germany E-mail: [email protected]

b Department of Theoretical Chemistry and Amsterdam Center for Multiscale Modeling, VU University Amsterdam, De Boelelaan 1083, NL-1081 HV Amsterdam, The Netherlands

c Institute of Molecules and Materials, Radboud University Nijmegen, Heyendaalseweg 135, NL-6525 AJ Nijmegen, The Netherlands E-mail: [email protected]

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.

Graphical abstract: Bite-angle bending as a key for understanding group-10 metal reactivity of d10-[M(NHC)2] complexes with sterically modest NHC ligands This article is Open Access Please wait while we load your content... About Cited by Related Download options Please wait...

Supplementary files

  • Supplementary information PDF (2994K)
  • Crystal structure data CIF (49K)

Article information

DOI https://doi.org/10.1039/C4SC02998D Article type Edge Article Submitted 29 Sep 2014 Accepted 03 Dec 2014 First published 03 Dec 2014 This article is Open Access All publication charges for this article have been paid for by the Royal Society of Chemistry Creative Commons BY-NC license

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Chem. Sci., 2015,6, 1426-1432 BibTex EndNote MEDLINE ProCite ReferenceManager RefWorks RIS

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Bite-angle bending as a key for understanding group-10 metal reactivity of d10-[M(NHC)2] complexes with sterically modest NHC ligands

F. Hering, J. Nitsch, U. Paul, A. Steffen, F. M. Bickelhaupt and U. Radius, Chem. Sci., 2015, 6, 1426 DOI: 10.1039/C4SC02998D

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