A Crystallographic Determination of the Influence of the Trans Ligand on the Bonding of Triphenylphosphine. Crystal and Molecular Structures of Cr(CO)4(PPh3)L (L = PBu3, P(OMe)3, and P(OPh)3)

Michael J. Wovkulich; Jerry L. Atwood; L. Canada; Jim D. Atwood

doi:10.1021/om00124a012

A Crystallographic Determination of the Influence of the Trans Ligand on the Bonding of Triphenylphosphine. Crystal and Molecular Structures of Cr(CO)₄(PPh₃)L (L = PBu₃, P(OMe)₃, and P(OPh)₃)

Michael J. Wovkulich
, Jerry L. Atwood
, L. Canada
, Jim D. Atwood

Chemistry

SUNY Buffalo
University of Alabama

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

32 Scopus citations

Abstract

The crystal structures of three complexes trans-Cr(CO)₄LPPh₃(L = PBu₃, P(OMe)_3,and P(OPh)₃) have been determined to define the influence of the trans ligand on the bonding of PPh₃. The Cr-PPh₃bond varies significantly with the trans ligand (L = PBu₃, Cr-PPh₃= 2.349 (4) A; L = P(OMe)₃, Cr-PPh₃= 2.364 (6) A; L = P(OPh)₃, Cr-PPh₃= 2.395 (2) A), shorter for a stronger donor in the trans position. This trans influence suggests a significant component of 7r-bonding in the Cr-PPh₃bond. The trans influence does not correlate with the kinetic trans effect for these complexes, indicating transition state effects dominate the reactivity. Chromium-phosphite and -phosphine bond lengths are compared.

Original language	English
Pages (from-to)	867-871
Number of pages	5
Journal	Organometallics
Volume	4
Issue number	5
DOIs	https://doi.org/10.1021/om00124a012
State	Published - May 1985

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@article{9113211d5b414b8994c0c97f1a5c8cfd,

title = "A Crystallographic Determination of the Influence of the Trans Ligand on the Bonding of Triphenylphosphine. Crystal and Molecular Structures of Cr(CO)4(PPh3)L (L = PBu3, P(OMe)3, and P(OPh)3)",

abstract = "The crystal structures of three complexes trans-Cr(CO)4LPPh3(L = PBu3, P(OMe)3,and P(OPh)3) have been determined to define the influence of the trans ligand on the bonding of PPh3. The Cr-PPh3bond varies significantly with the trans ligand (L = PBu3, Cr-PPh3= 2.349 (4) A; L = P(OMe)3, Cr-PPh3= 2.364 (6) A; L = P(OPh)3, Cr-PPh3= 2.395 (2) A), shorter for a stronger donor in the trans position. This trans influence suggests a significant component of 7r-bonding in the Cr-PPh3bond. The trans influence does not correlate with the kinetic trans effect for these complexes, indicating transition state effects dominate the reactivity. Chromium-phosphite and -phosphine bond lengths are compared.",

author = "Wovkulich, \{Michael J.\} and Atwood, \{Jerry L.\} and L. Canada and Atwood, \{Jim D.\}",

year = "1985",

month = may,

doi = "10.1021/om00124a012",

language = "English",

volume = "4",

pages = "867--871",

journal = "Organometallics",

issn = "0276-7333",

publisher = "American Chemical Society",

number = "5",

}

A Crystallographic Determination of the Influence of the Trans Ligand on the Bonding of Triphenylphosphine. Crystal and Molecular Structures of Cr(CO)₄(PPh₃)L (L = PBu₃, P(OMe)₃, and P(OPh)₃). / Wovkulich, Michael J.; Atwood, Jerry L.; Canada, L. et al.
In: Organometallics, Vol. 4, No. 5, 05.1985, p. 867-871.

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

TY - JOUR

T1 - A Crystallographic Determination of the Influence of the Trans Ligand on the Bonding of Triphenylphosphine. Crystal and Molecular Structures of Cr(CO)4(PPh3)L (L = PBu3, P(OMe)3, and P(OPh)3)

AU - Wovkulich, Michael J.

AU - Atwood, Jerry L.

AU - Canada, L.

AU - Atwood, Jim D.

PY - 1985/5

Y1 - 1985/5

N2 - The crystal structures of three complexes trans-Cr(CO)4LPPh3(L = PBu3, P(OMe)3,and P(OPh)3) have been determined to define the influence of the trans ligand on the bonding of PPh3. The Cr-PPh3bond varies significantly with the trans ligand (L = PBu3, Cr-PPh3= 2.349 (4) A; L = P(OMe)3, Cr-PPh3= 2.364 (6) A; L = P(OPh)3, Cr-PPh3= 2.395 (2) A), shorter for a stronger donor in the trans position. This trans influence suggests a significant component of 7r-bonding in the Cr-PPh3bond. The trans influence does not correlate with the kinetic trans effect for these complexes, indicating transition state effects dominate the reactivity. Chromium-phosphite and -phosphine bond lengths are compared.

AB - The crystal structures of three complexes trans-Cr(CO)4LPPh3(L = PBu3, P(OMe)3,and P(OPh)3) have been determined to define the influence of the trans ligand on the bonding of PPh3. The Cr-PPh3bond varies significantly with the trans ligand (L = PBu3, Cr-PPh3= 2.349 (4) A; L = P(OMe)3, Cr-PPh3= 2.364 (6) A; L = P(OPh)3, Cr-PPh3= 2.395 (2) A), shorter for a stronger donor in the trans position. This trans influence suggests a significant component of 7r-bonding in the Cr-PPh3bond. The trans influence does not correlate with the kinetic trans effect for these complexes, indicating transition state effects dominate the reactivity. Chromium-phosphite and -phosphine bond lengths are compared.

UR - https://www.scopus.com/pages/publications/0007738184

U2 - 10.1021/om00124a012

DO - 10.1021/om00124a012

M3 - Article

AN - SCOPUS:0007738184

SN - 0276-7333

VL - 4

SP - 867

EP - 871

JO - Organometallics

JF - Organometallics

IS - 5

ER -

A Crystallographic Determination of the Influence of the Trans Ligand on the Bonding of Triphenylphosphine. Crystal and Molecular Structures of Cr(CO)₄(PPh₃)L (L = PBu₃, P(OMe)₃, and P(OPh)₃)

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