EPR spectroscopic and theoretical study of chromium(I) carbonyl phosphine and phosphonite complexes

Derek A. Cummings; Jonathan McMaster; Anne L. Rieger; Philip H. Rieger

EPR spectroscopic and theoretical study of chromium(I) carbonyl phosphine and phosphonite complexes

Derek A. Cummings, Jonathan McMaster, Anne L. Rieger, Philip H. Rieger

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

Abstract

Isotropic and frozen-solution EPR spectra are reported for several Cr(I) carbonyl complexes of the type cis-[Cr(CO)₄L₂]⁺, mer- and fac-[Cr(CO)₃L₃]⁺, and trans-[Cr(CO)₂L₄]⁺, where L is a monodentate (or L₂ a bidentate) phosphine or phosphonite ligand. Extended Hückel molecular orbital theory calculations were performed for cis- and trans-[Cr(CO)₄L₂], mer-and fac-[Cr(CO)₃L₃], and cis- and trans-[Cr(CO)₂L₄] (L = PH₃, P(OH)₃). The EPR results are discussed in light of the electronic structure predictions, which also provide some insights on the oxidation potentials and the isomerization reaction energetics of these complexes. Isotropic ³¹P hyperfine couplings can be understood in terms of spin densities in the Cr 3d, P 3s, and P 3p orbitals.

Original language	English (US)
Pages (from-to)	4362-4368
Number of pages	7
Journal	Organometallics
Volume	16
Issue number	20
State	Published - Sep 30 1997
Externally published	Yes

ASJC Scopus subject areas

Inorganic Chemistry
Organic Chemistry

Cite this

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title = "EPR spectroscopic and theoretical study of chromium(I) carbonyl phosphine and phosphonite complexes",

abstract = "Isotropic and frozen-solution EPR spectra are reported for several Cr(I) carbonyl complexes of the type cis-[Cr(CO)4L2]+, mer- and fac-[Cr(CO)3L3]+, and trans-[Cr(CO)2L4]+, where L is a monodentate (or L2 a bidentate) phosphine or phosphonite ligand. Extended H{\"u}ckel molecular orbital theory calculations were performed for cis- and trans-[Cr(CO)4L2], mer-and fac-[Cr(CO)3L3], and cis- and trans-[Cr(CO)2L4] (L = PH3, P(OH)3). The EPR results are discussed in light of the electronic structure predictions, which also provide some insights on the oxidation potentials and the isomerization reaction energetics of these complexes. Isotropic 31P hyperfine couplings can be understood in terms of spin densities in the Cr 3d, P 3s, and P 3p orbitals.",

author = "Cummings, {Derek A.} and Jonathan McMaster and Rieger, {Anne L.} and Rieger, {Philip H.}",

year = "1997",

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language = "English (US)",

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pages = "4362--4368",

journal = "Organometallics",

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TY - JOUR

T1 - EPR spectroscopic and theoretical study of chromium(I) carbonyl phosphine and phosphonite complexes

AU - Cummings, Derek A.

AU - McMaster, Jonathan

AU - Rieger, Anne L.

AU - Rieger, Philip H.

PY - 1997/9/30

Y1 - 1997/9/30

N2 - Isotropic and frozen-solution EPR spectra are reported for several Cr(I) carbonyl complexes of the type cis-[Cr(CO)4L2]+, mer- and fac-[Cr(CO)3L3]+, and trans-[Cr(CO)2L4]+, where L is a monodentate (or L2 a bidentate) phosphine or phosphonite ligand. Extended Hückel molecular orbital theory calculations were performed for cis- and trans-[Cr(CO)4L2], mer-and fac-[Cr(CO)3L3], and cis- and trans-[Cr(CO)2L4] (L = PH3, P(OH)3). The EPR results are discussed in light of the electronic structure predictions, which also provide some insights on the oxidation potentials and the isomerization reaction energetics of these complexes. Isotropic 31P hyperfine couplings can be understood in terms of spin densities in the Cr 3d, P 3s, and P 3p orbitals.

AB - Isotropic and frozen-solution EPR spectra are reported for several Cr(I) carbonyl complexes of the type cis-[Cr(CO)4L2]+, mer- and fac-[Cr(CO)3L3]+, and trans-[Cr(CO)2L4]+, where L is a monodentate (or L2 a bidentate) phosphine or phosphonite ligand. Extended Hückel molecular orbital theory calculations were performed for cis- and trans-[Cr(CO)4L2], mer-and fac-[Cr(CO)3L3], and cis- and trans-[Cr(CO)2L4] (L = PH3, P(OH)3). The EPR results are discussed in light of the electronic structure predictions, which also provide some insights on the oxidation potentials and the isomerization reaction energetics of these complexes. Isotropic 31P hyperfine couplings can be understood in terms of spin densities in the Cr 3d, P 3s, and P 3p orbitals.

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AN - SCOPUS:0001075374

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ER -

EPR spectroscopic and theoretical study of chromium(I) carbonyl phosphine and phosphonite complexes

Abstract

ASJC Scopus subject areas

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