Relative Lability and Chemoselective Transmetallation of NHC in Hybrid Phosphine-NHC Ligands: Access to Heterometallic Complexes

Thomas Simler; Pierre Braunstein; Andreas A. Danopoulos

doi:10.1002/anie.201505958

Relative Lability and Chemoselective Transmetallation of NHC in Hybrid Phosphine-NHC Ligands: Access to Heterometallic Complexes

Thomas Simler
, Pierre Braunstein
, Andreas A. Danopoulos

Université de Strasbourg

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

Abstract

The relative lability and transmetallation aptitude of trialkylphosphine and NHC donors, integrated in semi-rigid hybrid ligands attached to [Ag₄Br₄] pseudo-cubanes, lies in favor of the NHC and is used to selectively access unprecedented NHC complexes with heterobimetallic cores, such as Ag-Cu (4^Cy) and Ag-Ir (5^tBu). These can be viewed as an arrested state before the full transmetallation of both donors, which gives the homodinuclear Cu (3^Cy) and Ir (6^Cy) complexes. The observed NHC transmetallation aptitude and reactivity urges caution in the common notion that views the NHC as a universal spectator.

Original language	English
Pages (from-to)	13691-13695
Number of pages	5
Journal	Angewandte Chemie - International Edition
Volume	54
Issue number	46
DOIs	https://doi.org/10.1002/anie.201505958
Publication status	Published - 1 Nov 2015
Externally published	Yes

Keywords

N-heterocyclic carbene
chemoselectivity
hybrid ligands
phosphines
transmetallation

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10.1002/anie.201505958

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title = "Relative Lability and Chemoselective Transmetallation of NHC in Hybrid Phosphine-NHC Ligands: Access to Heterometallic Complexes",

abstract = "The relative lability and transmetallation aptitude of trialkylphosphine and NHC donors, integrated in semi-rigid hybrid ligands attached to [Ag4Br4] pseudo-cubanes, lies in favor of the NHC and is used to selectively access unprecedented NHC complexes with heterobimetallic cores, such as Ag-Cu (4Cy) and Ag-Ir (5tBu). These can be viewed as an arrested state before the full transmetallation of both donors, which gives the homodinuclear Cu (3Cy) and Ir (6Cy) complexes. The observed NHC transmetallation aptitude and reactivity urges caution in the common notion that views the NHC as a universal spectator.",

keywords = "N-heterocyclic carbene, chemoselectivity, hybrid ligands, phosphines, transmetallation",

author = "Thomas Simler and Pierre Braunstein and Danopoulos, \{Andreas A.\}",

note = "Publisher Copyright: {\textcopyright} 2015 WILEY-VCH Verlag GmbH \& Co. KGaA, Weinheim.",

year = "2015",

month = nov,

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doi = "10.1002/anie.201505958",

language = "English",

volume = "54",

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journal = "Angewandte Chemie - International Edition",

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TY - JOUR

T1 - Relative Lability and Chemoselective Transmetallation of NHC in Hybrid Phosphine-NHC Ligands

T2 - Access to Heterometallic Complexes

AU - Simler, Thomas

AU - Braunstein, Pierre

AU - Danopoulos, Andreas A.

PY - 2015/11/1

Y1 - 2015/11/1

N2 - The relative lability and transmetallation aptitude of trialkylphosphine and NHC donors, integrated in semi-rigid hybrid ligands attached to [Ag4Br4] pseudo-cubanes, lies in favor of the NHC and is used to selectively access unprecedented NHC complexes with heterobimetallic cores, such as Ag-Cu (4Cy) and Ag-Ir (5tBu). These can be viewed as an arrested state before the full transmetallation of both donors, which gives the homodinuclear Cu (3Cy) and Ir (6Cy) complexes. The observed NHC transmetallation aptitude and reactivity urges caution in the common notion that views the NHC as a universal spectator.

AB - The relative lability and transmetallation aptitude of trialkylphosphine and NHC donors, integrated in semi-rigid hybrid ligands attached to [Ag4Br4] pseudo-cubanes, lies in favor of the NHC and is used to selectively access unprecedented NHC complexes with heterobimetallic cores, such as Ag-Cu (4Cy) and Ag-Ir (5tBu). These can be viewed as an arrested state before the full transmetallation of both donors, which gives the homodinuclear Cu (3Cy) and Ir (6Cy) complexes. The observed NHC transmetallation aptitude and reactivity urges caution in the common notion that views the NHC as a universal spectator.

KW - N-heterocyclic carbene

KW - chemoselectivity

KW - hybrid ligands

KW - phosphines

KW - transmetallation

U2 - 10.1002/anie.201505958

DO - 10.1002/anie.201505958

M3 - Article

AN - SCOPUS:84946228633

SN - 1433-7851

VL - 54

SP - 13691

EP - 13695

JO - Angewandte Chemie - International Edition

JF - Angewandte Chemie - International Edition

IS - 46

ER -

Relative Lability and Chemoselective Transmetallation of NHC in Hybrid Phosphine-NHC Ligands: Access to Heterometallic Complexes

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Keywords

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