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

doi:10.1039/c4sc02998d

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 Journal › Article › Academic › peer-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 language	English
Pages (from-to)	1426-1432
Number of pages	7
Journal	Chemical Science
Volume	6
Issue number	2
DOIs	https://doi.org/10.1039/c4sc02998d
Publication status	Published - 3 Dec 2014

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CCDC 1025171: Experimental Crystal Structure Determination
Hering, F. (Contributor), Nitsch, J. (Contributor), Paul, U. (Contributor), Steffen, A. (Contributor), Bickelhaupt, M. (Contributor) & Radius, U. (Contributor), Unknown Publisher, 1 Feb 2015
DOI: 10.5517/cc13ds1b, http://www.ccdc.cam.ac.uk/services/structure_request?id=doi:10.5517/cc13ds1b&sid=DataCite
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CCDC 1025170: Experimental Crystal Structure Determination
Hering, F. (Contributor), Nitsch, J. (Contributor), Paul, U. (Contributor), Steffen, A. (Contributor), Bickelhaupt, M. (Contributor) & Radius, U. (Contributor), Unknown Publisher, 1 Feb 2015
DOI: 10.5517/cc13ds09, http://www.ccdc.cam.ac.uk/services/structure_request?id=doi:10.5517/cc13ds09&sid=DataCite
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title = "Bite-angle bending as a key for understanding group-10 metal reactivity of d(10)-[M(NHC)(2)] complexes with sterically modest NHC ligands",

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.",

author = "Florian Hering and Joern Nitsch and Ursula Paul and Andreas Steffen and Bickelhaupt, {F. Matthias} and Udo Radius",

year = "2014",

month = dec,

day = "3",

doi = "10.1039/c4sc02998d",

language = "English",

volume = "6",

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journal = "Chemical Science",

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publisher = "Royal Society of Chemistry",

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TY - JOUR

T1 - Bite-angle bending as a key for understanding group-10 metal reactivity of d(10)-[M(NHC)(2)] complexes with sterically modest NHC ligands

AU - Hering, Florian

AU - Nitsch, Joern

AU - Paul, Ursula

AU - Steffen, Andreas

AU - Bickelhaupt, F. Matthias

AU - Radius, Udo

PY - 2014/12/3

Y1 - 2014/12/3

N2 - 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.

AB - 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.

U2 - 10.1039/c4sc02998d

DO - 10.1039/c4sc02998d

M3 - Article

SN - 2041-6520

VL - 6

SP - 1426

EP - 1432

JO - Chemical Science

JF - Chemical Science

IS - 2

ER -

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

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CCDC 1025171: Experimental Crystal Structure Determination

CCDC 1025170: Experimental Crystal Structure Determination

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