Coordination chemistry of higher oxidation states. 30. Five-coordinate cobalt(III) phosphine complexes. Spectroscopic ada cobalt K-edge EXAFS studies

William Levason; J. Steven Ogden; Mark D. Spicer

doi:10.1021/ic00310a022

Coordination chemistry of higher oxidation states. 30. Five-coordinate cobalt(III) phosphine complexes. Spectroscopic ada cobalt K-edge EXAFS studies

William Levason^*, J. Steven Ogden, Mark D. Spicer

^*Corresponding author for this work

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

19 Citations (Scopus)

Abstract

The complexes [Co(PR₃)₂X₃] (X = Cl, Br; PR₃= PMe₃, PEt₃, PMe2Ph, PEt₂Ph, PEtPh₂; X = Br, PR₃= PPh₃) have been prepared by oxidation of the corresponding [Co(PR₃)₂X₂] in dichloromethane with NOX at low temperatures. The intensely colored, paramagnetic (μ = 2.9-3.3 μ_B) Co(III) complexes are formulated as five-coordinate trigonal-bipyramidal species on the basis of vibrational and UV-visible spectroscopic studies and FAB mass spectra. Detailed assignments for the d-d and charge-transfer transitions in the UV-visible spectra are proposed. First-coordination-sphere bond lengths for the complexes [Co(PEt₃)₂X₃] and [Co(PEt₂Ph)₂X₃] were obtained by cobalt and bromine K-edge EXAFS spectroscopy (extended X-ray absorption fine structure), along with similar data for the model compounds [Co(PPh₃)₂X₂], For the cobalt(III) complexes average bond lengths are Co-P = 2.30 A, Co-Cl = 2.20 A, and Co-Br = 2.36 A.

Original language	English
Pages (from-to)	2128-2131
Number of pages	4
Journal	Inorganic Chemistry
Volume	28
Issue number	11
DOIs	https://doi.org/10.1021/ic00310a022
Publication status	Published - 1 May 1989
Externally published	Yes

ASJC Scopus subject areas

Physical and Theoretical Chemistry
Inorganic Chemistry

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@article{1083ba3810cb4c61909ced21a2632ce6,

title = "Coordination chemistry of higher oxidation states. 30. Five-coordinate cobalt(III) phosphine complexes. Spectroscopic ada cobalt K-edge EXAFS studies",

abstract = "The complexes [Co(PR3)2X3] (X = Cl, Br; PR3= PMe3, PEt3, PMe2Ph, PEt2Ph, PEtPh2; X = Br, PR3= PPh3) have been prepared by oxidation of the corresponding [Co(PR3)2X2] in dichloromethane with NOX at low temperatures. The intensely colored, paramagnetic (μ = 2.9-3.3 μB) Co(III) complexes are formulated as five-coordinate trigonal-bipyramidal species on the basis of vibrational and UV-visible spectroscopic studies and FAB mass spectra. Detailed assignments for the d-d and charge-transfer transitions in the UV-visible spectra are proposed. First-coordination-sphere bond lengths for the complexes [Co(PEt3)2X3] and [Co(PEt2Ph)2X3] were obtained by cobalt and bromine K-edge EXAFS spectroscopy (extended X-ray absorption fine structure), along with similar data for the model compounds [Co(PPh3)2X2], For the cobalt(III) complexes average bond lengths are Co-P = 2.30 A, Co-Cl = 2.20 A, and Co-Br = 2.36 A.",

author = "William Levason and Ogden, {J. Steven} and Spicer, {Mark D.}",

year = "1989",

month = may,

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doi = "10.1021/ic00310a022",

language = "English",

volume = "28",

pages = "2128--2131",

journal = "Inorganic Chemistry",

issn = "0020-1669",

publisher = "American Chemical Society",

number = "11",

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TY - JOUR

T1 - Coordination chemistry of higher oxidation states. 30. Five-coordinate cobalt(III) phosphine complexes. Spectroscopic ada cobalt K-edge EXAFS studies

AU - Levason, William

AU - Ogden, J. Steven

AU - Spicer, Mark D.

PY - 1989/5/1

Y1 - 1989/5/1

N2 - The complexes [Co(PR3)2X3] (X = Cl, Br; PR3= PMe3, PEt3, PMe2Ph, PEt2Ph, PEtPh2; X = Br, PR3= PPh3) have been prepared by oxidation of the corresponding [Co(PR3)2X2] in dichloromethane with NOX at low temperatures. The intensely colored, paramagnetic (μ = 2.9-3.3 μB) Co(III) complexes are formulated as five-coordinate trigonal-bipyramidal species on the basis of vibrational and UV-visible spectroscopic studies and FAB mass spectra. Detailed assignments for the d-d and charge-transfer transitions in the UV-visible spectra are proposed. First-coordination-sphere bond lengths for the complexes [Co(PEt3)2X3] and [Co(PEt2Ph)2X3] were obtained by cobalt and bromine K-edge EXAFS spectroscopy (extended X-ray absorption fine structure), along with similar data for the model compounds [Co(PPh3)2X2], For the cobalt(III) complexes average bond lengths are Co-P = 2.30 A, Co-Cl = 2.20 A, and Co-Br = 2.36 A.

AB - The complexes [Co(PR3)2X3] (X = Cl, Br; PR3= PMe3, PEt3, PMe2Ph, PEt2Ph, PEtPh2; X = Br, PR3= PPh3) have been prepared by oxidation of the corresponding [Co(PR3)2X2] in dichloromethane with NOX at low temperatures. The intensely colored, paramagnetic (μ = 2.9-3.3 μB) Co(III) complexes are formulated as five-coordinate trigonal-bipyramidal species on the basis of vibrational and UV-visible spectroscopic studies and FAB mass spectra. Detailed assignments for the d-d and charge-transfer transitions in the UV-visible spectra are proposed. First-coordination-sphere bond lengths for the complexes [Co(PEt3)2X3] and [Co(PEt2Ph)2X3] were obtained by cobalt and bromine K-edge EXAFS spectroscopy (extended X-ray absorption fine structure), along with similar data for the model compounds [Co(PPh3)2X2], For the cobalt(III) complexes average bond lengths are Co-P = 2.30 A, Co-Cl = 2.20 A, and Co-Br = 2.36 A.

U2 - 10.1021/ic00310a022

DO - 10.1021/ic00310a022

M3 - Article

AN - SCOPUS:0000637717

SN - 0020-1669

VL - 28

SP - 2128

EP - 2131

JO - Inorganic Chemistry

JF - Inorganic Chemistry

IS - 11

ER -

Coordination chemistry of higher oxidation states. 30. Five-coordinate cobalt(III) phosphine complexes. Spectroscopic ada cobalt K-edge EXAFS studies

Abstract

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