Iron and Cobalt Metallotropism in Remote-Substituted NHC Ligands: Metalation to Abnormal NHC Complexes or NHC Ring Opening

Andreas A. Danopoulos; Alexandre Massard; Gilles Frison; Pierre Braunstein

doi:10.1002/anie.201808008

Iron and Cobalt Metallotropism in Remote-Substituted NHC Ligands: Metalation to Abnormal NHC Complexes or NHC Ring Opening

Andreas A. Danopoulos
, Alexandre Massard
, Gilles Frison
, Pierre Braunstein

Université de Strasbourg
University of Athens
Université Paris-Saclay

Research output: Contribution to journal › Article › peer-review

Abstract

Metallotropism of the M[N(SiMe₃)₂]₂ metal fragment in the tautomeric system IA^R⇌AC^R involving imidazolium salts/N-heterocyclic carbenes with remote aminide/amine substituents, respectively, is manifested by its C_NHC carbophilicity (R=tBu, M=Co, Fe) or NR_aminido nitrogenophilicity (R=Cy, M=Co, Fe; R=Mes, M=Fe) and has been rationalized on the basis of steric and electronic effects. The thermolysis products of the [M{N(SiMe₃)₂}₂]/ IA^R⇌AC^R system are also substituent-dependent, leading to a rearranged aminide-functionalized aNHC Co₂ complex of an unprecedented type or to ring-opened metallaketenimines; they are postulated to originate from different metalloisomers. The results are interpreted on the basis of the X-ray diffraction analysis of 11 new compounds.

Original language	English
Pages (from-to)	14550-14554
Number of pages	5
Journal	Angewandte Chemie - International Edition
Volume	57
Issue number	44
DOIs	https://doi.org/10.1002/anie.201808008
Publication status	Published - 26 Oct 2018
Externally published	Yes

Keywords

N-heterocyclic carbenes
cobalt
dinuclear complex
iron
metallotropism

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10.1002/anie.201808008

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title = "Iron and Cobalt Metallotropism in Remote-Substituted NHC Ligands: Metalation to Abnormal NHC Complexes or NHC Ring Opening",

abstract = "Metallotropism of the M[N(SiMe3)2]2 metal fragment in the tautomeric system IAR⇌ACR involving imidazolium salts/N-heterocyclic carbenes with remote aminide/amine substituents, respectively, is manifested by its CNHC carbophilicity (R=tBu, M=Co, Fe) or NRaminido nitrogenophilicity (R=Cy, M=Co, Fe; R=Mes, M=Fe) and has been rationalized on the basis of steric and electronic effects. The thermolysis products of the [M\{N(SiMe3)2\}2]/ IAR⇌ACR system are also substituent-dependent, leading to a rearranged aminide-functionalized aNHC Co2 complex of an unprecedented type or to ring-opened metallaketenimines; they are postulated to originate from different metalloisomers. The results are interpreted on the basis of the X-ray diffraction analysis of 11 new compounds.",

keywords = "N-heterocyclic carbenes, cobalt, dinuclear complex, iron, metallotropism",

author = "Danopoulos, \{Andreas A.\} and Alexandre Massard and Gilles Frison and Pierre Braunstein",

note = "Publisher Copyright: {\textcopyright} 2018 Wiley-VCH Verlag GmbH \& Co. KGaA, Weinheim",

year = "2018",

month = oct,

day = "26",

doi = "10.1002/anie.201808008",

language = "English",

volume = "57",

pages = "14550--14554",

journal = "Angewandte Chemie - International Edition",

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TY - JOUR

T1 - Iron and Cobalt Metallotropism in Remote-Substituted NHC Ligands

T2 - Metalation to Abnormal NHC Complexes or NHC Ring Opening

AU - Danopoulos, Andreas A.

AU - Massard, Alexandre

AU - Frison, Gilles

AU - Braunstein, Pierre

PY - 2018/10/26

Y1 - 2018/10/26

N2 - Metallotropism of the M[N(SiMe3)2]2 metal fragment in the tautomeric system IAR⇌ACR involving imidazolium salts/N-heterocyclic carbenes with remote aminide/amine substituents, respectively, is manifested by its CNHC carbophilicity (R=tBu, M=Co, Fe) or NRaminido nitrogenophilicity (R=Cy, M=Co, Fe; R=Mes, M=Fe) and has been rationalized on the basis of steric and electronic effects. The thermolysis products of the [M{N(SiMe3)2}2]/ IAR⇌ACR system are also substituent-dependent, leading to a rearranged aminide-functionalized aNHC Co2 complex of an unprecedented type or to ring-opened metallaketenimines; they are postulated to originate from different metalloisomers. The results are interpreted on the basis of the X-ray diffraction analysis of 11 new compounds.

AB - Metallotropism of the M[N(SiMe3)2]2 metal fragment in the tautomeric system IAR⇌ACR involving imidazolium salts/N-heterocyclic carbenes with remote aminide/amine substituents, respectively, is manifested by its CNHC carbophilicity (R=tBu, M=Co, Fe) or NRaminido nitrogenophilicity (R=Cy, M=Co, Fe; R=Mes, M=Fe) and has been rationalized on the basis of steric and electronic effects. The thermolysis products of the [M{N(SiMe3)2}2]/ IAR⇌ACR system are also substituent-dependent, leading to a rearranged aminide-functionalized aNHC Co2 complex of an unprecedented type or to ring-opened metallaketenimines; they are postulated to originate from different metalloisomers. The results are interpreted on the basis of the X-ray diffraction analysis of 11 new compounds.

KW - N-heterocyclic carbenes

KW - cobalt

KW - dinuclear complex

KW - iron

KW - metallotropism

U2 - 10.1002/anie.201808008

DO - 10.1002/anie.201808008

M3 - Article

C2 - 30182525

AN - SCOPUS:85053495860

SN - 1433-7851

VL - 57

SP - 14550

EP - 14554

JO - Angewandte Chemie - International Edition

JF - Angewandte Chemie - International Edition

IS - 44

ER -

Iron and Cobalt Metallotropism in Remote-Substituted NHC Ligands: Metalation to Abnormal NHC Complexes or NHC Ring Opening

Abstract

Keywords

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