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N -Heterocyclic carbene and cyclic (alkyl)(amino)carbene complexes of vanadium(III) and vanadium(V).

Authors :
Horrer G
Krummenacher I
Mann S
Braunschweig H
Radius U
Source :
Dalton transactions (Cambridge, England : 2003) [Dalton Trans] 2022 Jul 26; Vol. 51 (29), pp. 11054-11071. Date of Electronic Publication: 2022 Jul 26.
Publication Year :
2022

Abstract

[VCl <subscript>3</subscript> (THF) <subscript>3</subscript> ] offers a convenient entrance point into the chemistry of carbene stabilized V(III) complexes. Herein we report the paramagnetic mono- and biscarbene complexes [VCl <subscript>3</subscript> (cAAC <superscript>Me</superscript> )] 1, [VCl <subscript>3</subscript> (cAAC <superscript>Me</superscript> )(THF)] 1(thf), [VCl <subscript>3</subscript> (IMes)] 2, [{VCl <subscript>2</subscript> (IiPr <superscript>Me</superscript> )(μ-Cl)} <subscript>2</subscript> ] 3, [VCl <subscript>3</subscript> (IDipp)] 4, [VCl <subscript>3</subscript> (SIDipp)] 5, [VCl <subscript>3</subscript> (SIDipp)(THF)] 5(thf), [VCl <subscript>3</subscript> (I t Bu)] 6, [VCl <subscript>3</subscript> (cAAC <superscript>Me</superscript> ) <subscript>2</subscript> ] 7 and [VCl <subscript>3</subscript> (IiPr <superscript>Me</superscript> ) <subscript>2</subscript> ] 8. Reaction of 1 with MesMgCl, MesLi and LiNPh <subscript>2</subscript> afforded the complexes [VCl <subscript>2</subscript> (Mes)(cAAC <superscript>Me</superscript> )] 9, [cAAC <superscript>Me</superscript> H] <superscript>+</superscript> [VCl <subscript>2</subscript> Mes <subscript>2</subscript> ] <superscript>-</superscript> 10 and [VCl <subscript>2</subscript> (NPh <subscript>2</subscript> )(cAAC <superscript>Me</superscript> )] 11. The V(V) complexes [V(O)Cl <subscript>3</subscript> (IDipp)] 12 and [V(O)Cl <subscript>3</subscript> (SIDipp)] 13 were selectively prepared from oxygen oxidation of 4 and 5. [V(O)Cl <subscript>3</subscript> (IDipp)] 12 and [V(O)Cl <subscript>3</subscript> (IMes)] react with isocyanates to yield the NHC-ligated imido complexes [V(N- p -CH <subscript>3</subscript> C <subscript>6</subscript> H <subscript>4</subscript> )Cl <subscript>3</subscript> (IDipp)] 14, [V(N- p -FC <subscript>6</subscript> H <subscript>4</subscript> )Cl <subscript>3</subscript> (IDipp)] 15, [V(N- p -CH <subscript>3</subscript> C <subscript>6</subscript> H <subscript>4</subscript> )Cl <subscript>3</subscript> (SIDipp)] 16, [V(N- p -FC <subscript>6</subscript> H <subscript>4</subscript> )Cl <subscript>3</subscript> (SIDipp)] 17, [V(N- p -CH <subscript>3</subscript> C <subscript>6</subscript> H <subscript>4</subscript> )Cl <subscript>3</subscript> (IMes)] 18 and [V(N- p -FC <subscript>6</subscript> H <subscript>4</subscript> )Cl <subscript>3</subscript> (IMes)] 19.

Details

Language :
English
ISSN :
1477-9234
Volume :
51
Issue :
29
Database :
MEDLINE
Journal :
Dalton transactions (Cambridge, England : 2003)
Publication Type :
Academic Journal
Accession number :
35796195
Full Text :
https://doi.org/10.1039/d2dt01250b