Reduction of π-bound nitriles to π-bound imines in a tungsten(II) bis(acetylacetonate) coordination sphere

Andrew B. Jackson; Chetna Khosla; Helen E. Gaskins; Peter S. White; Joseph L. Templeton

doi:10.1021/om7009039

Reduction of π-bound nitriles to π-bound imines in a tungsten(II) bis(acetylacetonate) coordination sphere

Andrew B. Jackson, Chetna Khosla, Helen E. Gaskins, Peter S. White, Joseph L. Templeton

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

15 Scopus citations

Abstract

Addition of MeOTf (OTf = CF₃SO₃) to complexes of the type W(CO)(acac)₂(η²-N≡CR) (acac = acetylacetonate) [R = Ph (1a), Me (1b)] yields cationic iminoacyl triflate salts of the type [W(CO)-(acac)₂(η²-MeN=CR)][OTf]. Complexes 2a and 2b undergo nucleophilic attack at the iminoacyl carbon with Na[HB(OMe)₃] or MeMgBr to form neutral η²-imine complexes of the type W(CO)(acac)₂[η²-MeN=C(Nuc)R] [Nuc = H (3a, 3b), Me (4)]. Hydride addition to 2b results in W(CO)(acac) ₂(η²-MeN=CHMe), 3b, a complex that exhibits interconversion of diastereomers at ambient temperature on the NMR time scale. X-ray structures of cationic iminoacyl complex 2a and neutral imine complex 4 confirm η²-C=N bonding of both the iminoacyl and imine ligands.

Original language	English (US)
Pages (from-to)	1322-1327
Number of pages	6
Journal	Organometallics
Volume	27
Issue number	6
DOIs	https://doi.org/10.1021/om7009039
State	Published - Mar 24 2008
Externally published	Yes

ASJC Scopus subject areas

Physical and Theoretical Chemistry
Organic Chemistry
Inorganic Chemistry

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title = "Reduction of π-bound nitriles to π-bound imines in a tungsten(II) bis(acetylacetonate) coordination sphere",

abstract = "Addition of MeOTf (OTf = CF3SO3) to complexes of the type W(CO)(acac)2(η2-N≡CR) (acac = acetylacetonate) [R = Ph (1a), Me (1b)] yields cationic iminoacyl triflate salts of the type [W(CO)-(acac)2(η2-MeN=CR)][OTf]. Complexes 2a and 2b undergo nucleophilic attack at the iminoacyl carbon with Na[HB(OMe)3] or MeMgBr to form neutral η2-imine complexes of the type W(CO)(acac)2[η2-MeN=C(Nuc)R] [Nuc = H (3a, 3b), Me (4)]. Hydride addition to 2b results in W(CO)(acac) 2(η2-MeN=CHMe), 3b, a complex that exhibits interconversion of diastereomers at ambient temperature on the NMR time scale. X-ray structures of cationic iminoacyl complex 2a and neutral imine complex 4 confirm η2-C=N bonding of both the iminoacyl and imine ligands.",

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AU - Jackson, Andrew B.

AU - Khosla, Chetna

AU - Gaskins, Helen E.

AU - White, Peter S.

AU - Templeton, Joseph L.

PY - 2008/3/24

Y1 - 2008/3/24

N2 - Addition of MeOTf (OTf = CF3SO3) to complexes of the type W(CO)(acac)2(η2-N≡CR) (acac = acetylacetonate) [R = Ph (1a), Me (1b)] yields cationic iminoacyl triflate salts of the type [W(CO)-(acac)2(η2-MeN=CR)][OTf]. Complexes 2a and 2b undergo nucleophilic attack at the iminoacyl carbon with Na[HB(OMe)3] or MeMgBr to form neutral η2-imine complexes of the type W(CO)(acac)2[η2-MeN=C(Nuc)R] [Nuc = H (3a, 3b), Me (4)]. Hydride addition to 2b results in W(CO)(acac) 2(η2-MeN=CHMe), 3b, a complex that exhibits interconversion of diastereomers at ambient temperature on the NMR time scale. X-ray structures of cationic iminoacyl complex 2a and neutral imine complex 4 confirm η2-C=N bonding of both the iminoacyl and imine ligands.

AB - Addition of MeOTf (OTf = CF3SO3) to complexes of the type W(CO)(acac)2(η2-N≡CR) (acac = acetylacetonate) [R = Ph (1a), Me (1b)] yields cationic iminoacyl triflate salts of the type [W(CO)-(acac)2(η2-MeN=CR)][OTf]. Complexes 2a and 2b undergo nucleophilic attack at the iminoacyl carbon with Na[HB(OMe)3] or MeMgBr to form neutral η2-imine complexes of the type W(CO)(acac)2[η2-MeN=C(Nuc)R] [Nuc = H (3a, 3b), Me (4)]. Hydride addition to 2b results in W(CO)(acac) 2(η2-MeN=CHMe), 3b, a complex that exhibits interconversion of diastereomers at ambient temperature on the NMR time scale. X-ray structures of cationic iminoacyl complex 2a and neutral imine complex 4 confirm η2-C=N bonding of both the iminoacyl and imine ligands.

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Reduction of π-bound nitriles to π-bound imines in a tungsten(II) bis(acetylacetonate) coordination sphere

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