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N-Heterocyclic carbene and cyclic (alkyl)(amino)carbene ligated half-sandwich complexes of chromium(II) and chromium(I).

Authors :
Horrer, Günther
Luff, Martin S.
Radius, Udo
Source :
Dalton Transactions: An International Journal of Inorganic Chemistry; 10/7/2023, Vol. 52 Issue 37, p13244-13257, 14p
Publication Year :
2023

Abstract

The synthesis and characterization of a series of Cr(II) N-Heterocyclic Carbene (NHC) complexes of the type [{Cr(NHC)Cl(μ-Cl)}<subscript>2</subscript>] and [(Cyp)Cr(NHC)X] (Cyp = η<superscript>5</superscript>-C<subscript>5</subscript>H<subscript>5</subscript>, cyclopentadienyl; η<superscript>5</superscript>-C<subscript>5</subscript>Me<subscript>5</subscript>, pentamethylcyclopentadienyl; X = Cl, η<superscript>3</superscript>-C<subscript>3</subscript>H<subscript>5</subscript>; NHC = IMe<superscript>Me</superscript>, IiPr<superscript>Me</superscript>, IMes, IDipp) as well as the cyclic (alkyl)(amino)carbene cAAC<superscript>Me</superscript> ligated complexes [(η<superscript>5</superscript>-C<subscript>5</subscript>H<subscript>5</subscript>)Cr(cAAC<superscript>Me</superscript>)X] (X = Cl, NPh<subscript>2</subscript>), [(η<superscript>5</superscript>-C<subscript>9</subscript>H<subscript>7</subscript>)Cr(cAAC<superscript>Me</superscript>)Cl] (C<subscript>9</subscript>H<subscript>7</subscript> = Ind, indenyl) and [(η<superscript>5</superscript>-C<subscript>13</subscript>H<subscript>9</subscript>)Cr(cAAC<superscript>Me</superscript>)Cl] (C<subscript>13</subscript>H<subscript>9</subscript> = Fl, fluorenyl) are reported. The reduction of [(η<superscript>5</superscript>-C<subscript>5</subscript>Me<subscript>5</subscript>)Cr(IMe<superscript>Me</superscript>)Cl] with KC<subscript>8</subscript> in the presence of CO afforded the NHC ligated Cr(I) metallo-radical [(η<superscript>5</superscript>-C<subscript>5</subscript>Me<subscript>5</subscript>)Cr(IMe<superscript>Me</superscript>)(CO)<subscript>2</subscript>]. Quantum chemical calculations performed on [(η<superscript>5</superscript>-C<subscript>5</subscript>Me<subscript>5</subscript>)Cr(IMe<superscript>Me</superscript>)(CO)<subscript>2</subscript>] confirm for this complex a predominantly chromium centered radical. [ABSTRACT FROM AUTHOR]

Details

Language :
English
ISSN :
14779226
Volume :
52
Issue :
37
Database :
Complementary Index
Journal :
Dalton Transactions: An International Journal of Inorganic Chemistry
Publication Type :
Academic Journal
Accession number :
172334023
Full Text :
https://doi.org/10.1039/d3dt02123h