A tungsten-183 NMR study of cis and trans isomers of [W(CO) 4(PPh3)(PR3)](PR3 = phosphine, phosphite)

Laurence Carlton; Avril Emdin; Andreas Lemmerer; Manuel A. Fernandes

doi:10.1002/mrc.2300

A tungsten-183 NMR study of cis and trans isomers of [W(CO) ₄(PPh₃)(PR₃)](PR₃ = phosphine, phosphite)

Laurence Carlton, Avril Emdin, Andreas Lemmerer, Manuel A. Fernandes

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

10 Scopus citations

Abstract

Tungsten-183 NMR data are reported for the complexes cis- and trans-[W(CO)₄(PPh₃)(PR₃)] (PR₃ = PⁿBu₃, PMe₃, PMe₂Ph, PMePh ₂, PPh₃, P(4-C₆H₄OMe)₃, P(4-C₆H₄Me)₃, P(4-C₆H ₄F)₃, P(OMe)₃, P(OEt)₃, P(OPh) ₃ and for PCy₃, P(NMe₂)₃(trans isomer only). The ¹⁸³W chemical shift (obtained by indirect detection using ³¹P) is found to be related to the PR₃ ligand parameters ν and θ (Tolman electronic factor and cone angle, respectively) for the cis isomers and to ν (but only poorly to θ) for the trans isomers. The ¹⁸³W-³¹P spin coupling constant is also related, less clearly for P-C than for P-N and P-O bonded ligands, to ν. Chemical shifts are referenced to an absolute frequency Ξ (¹⁸³W) = 4.15 MHz, which is proposed as a calibration standard for ¹⁸³W NMR. The structures of cis-[W(CO)₄(PPh₃)(PMe₃)] and cis-[W(CO)₄(PPh₃){P(4-C₆H₄F) ₃}] are reported.

Original language	English
Pages (from-to)	S56-S62
Journal	Magnetic Resonance in Chemistry
Volume	46
Issue number	SUPPL. 1
DOIs	https://doi.org/10.1002/mrc.2300
State	Published - 1 Jan 2008
Externally published	Yes

Keywords

W NMR
P NMR
Chemical shift
Crystal structure
Phosphines
Tungsten complexes

ASJC Scopus subject areas

General Chemistry
General Materials Science

Access to Document

10.1002/mrc.2300

Cite this

@article{88a1901e97b04d73875d90b538938b02,

title = "A tungsten-183 NMR study of cis and trans isomers of [W(CO) 4(PPh3)(PR3)](PR3 = phosphine, phosphite)",

abstract = "Tungsten-183 NMR data are reported for the complexes cis- and trans-[W(CO)4(PPh3)(PR3)] (PR3 = PnBu3, PMe3, PMe2Ph, PMePh 2, PPh3, P(4-C6H4OMe)3, P(4-C6H4Me)3, P(4-C6H 4F)3, P(OMe)3, P(OEt)3, P(OPh) 3 and for PCy3, P(NMe2)3(trans isomer only). The 183W chemical shift (obtained by indirect detection using 31P) is found to be related to the PR3 ligand parameters ν and θ (Tolman electronic factor and cone angle, respectively) for the cis isomers and to ν (but only poorly to θ) for the trans isomers. The 183W-31P spin coupling constant is also related, less clearly for P-C than for P-N and P-O bonded ligands, to ν. Chemical shifts are referenced to an absolute frequency Ξ (183W) = 4.15 MHz, which is proposed as a calibration standard for 183W NMR. The structures of cis-[W(CO)4(PPh3)(PMe3)] and cis-[W(CO)4(PPh3){P(4-C6H4F) 3}] are reported.",

keywords = "W NMR, P NMR, Chemical shift, Crystal structure, Phosphines, Tungsten complexes",

author = "Laurence Carlton and Avril Emdin and Andreas Lemmerer and Fernandes, {Manuel A.}",

year = "2008",

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T1 - A tungsten-183 NMR study of cis and trans isomers of [W(CO) 4(PPh3)(PR3)](PR3 = phosphine, phosphite)

AU - Carlton, Laurence

AU - Emdin, Avril

AU - Lemmerer, Andreas

AU - Fernandes, Manuel A.

PY - 2008/1/1

Y1 - 2008/1/1

N2 - Tungsten-183 NMR data are reported for the complexes cis- and trans-[W(CO)4(PPh3)(PR3)] (PR3 = PnBu3, PMe3, PMe2Ph, PMePh 2, PPh3, P(4-C6H4OMe)3, P(4-C6H4Me)3, P(4-C6H 4F)3, P(OMe)3, P(OEt)3, P(OPh) 3 and for PCy3, P(NMe2)3(trans isomer only). The 183W chemical shift (obtained by indirect detection using 31P) is found to be related to the PR3 ligand parameters ν and θ (Tolman electronic factor and cone angle, respectively) for the cis isomers and to ν (but only poorly to θ) for the trans isomers. The 183W-31P spin coupling constant is also related, less clearly for P-C than for P-N and P-O bonded ligands, to ν. Chemical shifts are referenced to an absolute frequency Ξ (183W) = 4.15 MHz, which is proposed as a calibration standard for 183W NMR. The structures of cis-[W(CO)4(PPh3)(PMe3)] and cis-[W(CO)4(PPh3){P(4-C6H4F) 3}] are reported.

AB - Tungsten-183 NMR data are reported for the complexes cis- and trans-[W(CO)4(PPh3)(PR3)] (PR3 = PnBu3, PMe3, PMe2Ph, PMePh 2, PPh3, P(4-C6H4OMe)3, P(4-C6H4Me)3, P(4-C6H 4F)3, P(OMe)3, P(OEt)3, P(OPh) 3 and for PCy3, P(NMe2)3(trans isomer only). The 183W chemical shift (obtained by indirect detection using 31P) is found to be related to the PR3 ligand parameters ν and θ (Tolman electronic factor and cone angle, respectively) for the cis isomers and to ν (but only poorly to θ) for the trans isomers. The 183W-31P spin coupling constant is also related, less clearly for P-C than for P-N and P-O bonded ligands, to ν. Chemical shifts are referenced to an absolute frequency Ξ (183W) = 4.15 MHz, which is proposed as a calibration standard for 183W NMR. The structures of cis-[W(CO)4(PPh3)(PMe3)] and cis-[W(CO)4(PPh3){P(4-C6H4F) 3}] are reported.

KW - W NMR

KW - P NMR

KW - Chemical shift

KW - Crystal structure

KW - Phosphines

KW - Tungsten complexes

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