A first structural and theoretical comparison of pyridinylidene-type rNHC (remote N-heterocyclic carbene) and NHC complexes of Ni(II) obtained by oxidative substitution

Sabine K. Schneider; Gerrit R. Julius; Christoph Loschen; Helgard G. Raubenheimer; Gernot Frenking; Wolfgang A. Herrmann

doi:10.1039/b512419k

A first structural and theoretical comparison of pyridinylidene-type rNHC (remote N-heterocyclic carbene) and NHC complexes of Ni(II) obtained by oxidative substitution

Sabine K. Schneider, Gerrit R. Julius, Christoph Loschen, Helgard G. Raubenheimer, Gernot Frenking, Wolfgang A. Herrmann

Technical University of Munich

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

71 Scopus citations

Abstract

A series of cationic pyridinylidene and quinolinylidene complexes of chlorobis(triphenylphosphine)nickel(ii) were prepared by oxidative substitution of Ni(PPh₃)₄ with methylated chloropyridines or chloroquinolines. NMR as well as X-ray crystallographic studies confirmed the trans arrangement of the two phosphines in the products. Calculations, using suitable model compounds at the BP86/TZVP level, clearly differentiate between a standard imidazolylidene complex and new complexes of the NHC-type on the one hand, and new complexes classified as rNHC-types - with the heteroatom distant from the carbene carbon - on the other. The latter form significantly stronger bonds - mainly of an electrostatic nature - with the metal.

Original language	English
Pages (from-to)	1226-1233
Number of pages	8
Journal	Dalton Transactions
Volume	6
Issue number	9
DOIs	https://doi.org/10.1039/b512419k
State	Published - 2006

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title = "A first structural and theoretical comparison of pyridinylidene-type rNHC (remote N-heterocyclic carbene) and NHC complexes of Ni(II) obtained by oxidative substitution",

abstract = "A series of cationic pyridinylidene and quinolinylidene complexes of chlorobis(triphenylphosphine)nickel(ii) were prepared by oxidative substitution of Ni(PPh3)4 with methylated chloropyridines or chloroquinolines. NMR as well as X-ray crystallographic studies confirmed the trans arrangement of the two phosphines in the products. Calculations, using suitable model compounds at the BP86/TZVP level, clearly differentiate between a standard imidazolylidene complex and new complexes of the NHC-type on the one hand, and new complexes classified as rNHC-types - with the heteroatom distant from the carbene carbon - on the other. The latter form significantly stronger bonds - mainly of an electrostatic nature - with the metal.",

author = "Schneider, {Sabine K.} and Julius, {Gerrit R.} and Christoph Loschen and Raubenheimer, {Helgard G.} and Gernot Frenking and Herrmann, {Wolfgang A.}",

year = "2006",

doi = "10.1039/b512419k",

language = "English",

volume = "6",

pages = "1226--1233",

journal = "Dalton Transactions",

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T1 - A first structural and theoretical comparison of pyridinylidene-type rNHC (remote N-heterocyclic carbene) and NHC complexes of Ni(II) obtained by oxidative substitution

AU - Schneider, Sabine K.

AU - Julius, Gerrit R.

AU - Loschen, Christoph

AU - Raubenheimer, Helgard G.

AU - Frenking, Gernot

AU - Herrmann, Wolfgang A.

PY - 2006

Y1 - 2006

N2 - A series of cationic pyridinylidene and quinolinylidene complexes of chlorobis(triphenylphosphine)nickel(ii) were prepared by oxidative substitution of Ni(PPh3)4 with methylated chloropyridines or chloroquinolines. NMR as well as X-ray crystallographic studies confirmed the trans arrangement of the two phosphines in the products. Calculations, using suitable model compounds at the BP86/TZVP level, clearly differentiate between a standard imidazolylidene complex and new complexes of the NHC-type on the one hand, and new complexes classified as rNHC-types - with the heteroatom distant from the carbene carbon - on the other. The latter form significantly stronger bonds - mainly of an electrostatic nature - with the metal.

AB - A series of cationic pyridinylidene and quinolinylidene complexes of chlorobis(triphenylphosphine)nickel(ii) were prepared by oxidative substitution of Ni(PPh3)4 with methylated chloropyridines or chloroquinolines. NMR as well as X-ray crystallographic studies confirmed the trans arrangement of the two phosphines in the products. Calculations, using suitable model compounds at the BP86/TZVP level, clearly differentiate between a standard imidazolylidene complex and new complexes of the NHC-type on the one hand, and new complexes classified as rNHC-types - with the heteroatom distant from the carbene carbon - on the other. The latter form significantly stronger bonds - mainly of an electrostatic nature - with the metal.

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U2 - 10.1039/b512419k

DO - 10.1039/b512419k

M3 - Article

AN - SCOPUS:32944476180

SN - 1477-9226

VL - 6

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JO - Dalton Transactions

JF - Dalton Transactions

IS - 9

ER -

A first structural and theoretical comparison of pyridinylidene-type rNHC (remote N-heterocyclic carbene) and NHC complexes of Ni(II) obtained by oxidative substitution

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