Ligand-mediated metal-metal interactions in (ν5:ν5-fulvalene) bis (dicarbonylcobalt) and rhodium complexes

Dennis L. Lichtenberger; Nadine E. Gruhn; Margaret E. Rempe; William E. Geiger; Teen T. Chin

doi:10.1016/0020-1693(95)04591-0

Ligand-mediated metal-metal interactions in (ν⁵:ν⁵-fulvalene) bis (dicarbonylcobalt) and rhodium complexes

Dennis L. Lichtenberger, Nadine E. Gruhn, Margaret E. Rempe, William E. Geiger, Teen T. Chin

Chemistry and Biochemistry

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

10 Scopus citations

Abstract

Gas phase photoelectron spectroscopy (PES) is used to investigate the bonding and electronic structure in (fv) [M(CO)₂]₂ (fv = fulvalene, η⁵:η⁵-C₁₀H₈^2-; M = Co, Rh). The results for these bimetallic complexes are also compared to those for the analogous monometallic complexes CpM(CO)₂ (Cp = η⁵-C₅H₅^-; M = Co, Rh) which have been reported previously. The low valence ionization patterns observed for CpCo(CO)₂ and (fv)[Co(CO)₂]₂ are very similar, indicating that there is little electronic interaction between the two metals of the dicobalt complex. The spectrum of (fv)[Rh(CO)₂]₂ also is very similar to the spectrum of CpRh(CO)₂, except that the first metal ionizations in the bimetallic rhodium compound show a significant splitting (0.45 eV). This splitting is due to electronic interaction between the two metal centers which occurs via communication through the fulvalene π system. The differences in electronic structure are compared to the differences in electrochemical behavior of the Co and Rh fulvalene complexes.

Original language	English (US)
Pages (from-to)	623-629
Number of pages	7
Journal	Inorganica Chimica Acta
Volume	240
Issue number	1-2
DOIs	https://doi.org/10.1016/0020-1693(95)04591-0
State	Published - Dec 1995

Keywords

Bimetallic complexes
Cobalt complexes
Fulvalene complexes
Gas phase photoelectron spectroscopy
Rhodium complexes

ASJC Scopus subject areas

Physical and Theoretical Chemistry
Inorganic Chemistry
Materials Chemistry

Access to Document

10.1016/0020-1693(95)04591-0

Cite this

@article{acb5a8d8862b42a2993dc3fde2c0127a,

title = "Ligand-mediated metal-metal interactions in (ν5:ν5-fulvalene) bis (dicarbonylcobalt) and rhodium complexes",

abstract = "Gas phase photoelectron spectroscopy (PES) is used to investigate the bonding and electronic structure in (fv) [M(CO)2]2 (fv = fulvalene, η5:η5-C10H82-; M = Co, Rh). The results for these bimetallic complexes are also compared to those for the analogous monometallic complexes CpM(CO)2 (Cp = η5-C5H5-; M = Co, Rh) which have been reported previously. The low valence ionization patterns observed for CpCo(CO)2 and (fv)[Co(CO)2]2 are very similar, indicating that there is little electronic interaction between the two metals of the dicobalt complex. The spectrum of (fv)[Rh(CO)2]2 also is very similar to the spectrum of CpRh(CO)2, except that the first metal ionizations in the bimetallic rhodium compound show a significant splitting (0.45 eV). This splitting is due to electronic interaction between the two metal centers which occurs via communication through the fulvalene π system. The differences in electronic structure are compared to the differences in electrochemical behavior of the Co and Rh fulvalene complexes.",

keywords = "Bimetallic complexes, Cobalt complexes, Fulvalene complexes, Gas phase photoelectron spectroscopy, Rhodium complexes",

author = "Lichtenberger, {Dennis L.} and Gruhn, {Nadine E.} and Rempe, {Margaret E.} and Geiger, {William E.} and Chin, {Teen T.}",

note = "Funding Information: D.L.L. acknowledges support by the US Department of Energy (Division of Chemical Sciences, Office of Basic Energy Sciences, Office of Energy Research, DF-SG02-86ER13501), the National Science Foundation (Grant No. CHE93-00841) for contributions to the equipment, and the Materials Characterization Program, Department of Chemistry, University of Arizona. W.E.G. acknowledges support by the National Science Foundation (Grant No. CHE 91-16332).",

year = "1995",

month = dec,

doi = "10.1016/0020-1693(95)04591-0",

language = "English (US)",

volume = "240",

pages = "623--629",

journal = "Inorganica Chimica Acta",

issn = "0020-1693",

publisher = "Elsevier BV",

number = "1-2",

}

TY - JOUR

T1 - Ligand-mediated metal-metal interactions in (ν5:ν5-fulvalene) bis (dicarbonylcobalt) and rhodium complexes

AU - Lichtenberger, Dennis L.

AU - Gruhn, Nadine E.

AU - Rempe, Margaret E.

AU - Geiger, William E.

AU - Chin, Teen T.

N1 - Funding Information: D.L.L. acknowledges support by the US Department of Energy (Division of Chemical Sciences, Office of Basic Energy Sciences, Office of Energy Research, DF-SG02-86ER13501), the National Science Foundation (Grant No. CHE93-00841) for contributions to the equipment, and the Materials Characterization Program, Department of Chemistry, University of Arizona. W.E.G. acknowledges support by the National Science Foundation (Grant No. CHE 91-16332).

PY - 1995/12

Y1 - 1995/12

N2 - Gas phase photoelectron spectroscopy (PES) is used to investigate the bonding and electronic structure in (fv) [M(CO)2]2 (fv = fulvalene, η5:η5-C10H82-; M = Co, Rh). The results for these bimetallic complexes are also compared to those for the analogous monometallic complexes CpM(CO)2 (Cp = η5-C5H5-; M = Co, Rh) which have been reported previously. The low valence ionization patterns observed for CpCo(CO)2 and (fv)[Co(CO)2]2 are very similar, indicating that there is little electronic interaction between the two metals of the dicobalt complex. The spectrum of (fv)[Rh(CO)2]2 also is very similar to the spectrum of CpRh(CO)2, except that the first metal ionizations in the bimetallic rhodium compound show a significant splitting (0.45 eV). This splitting is due to electronic interaction between the two metal centers which occurs via communication through the fulvalene π system. The differences in electronic structure are compared to the differences in electrochemical behavior of the Co and Rh fulvalene complexes.

AB - Gas phase photoelectron spectroscopy (PES) is used to investigate the bonding and electronic structure in (fv) [M(CO)2]2 (fv = fulvalene, η5:η5-C10H82-; M = Co, Rh). The results for these bimetallic complexes are also compared to those for the analogous monometallic complexes CpM(CO)2 (Cp = η5-C5H5-; M = Co, Rh) which have been reported previously. The low valence ionization patterns observed for CpCo(CO)2 and (fv)[Co(CO)2]2 are very similar, indicating that there is little electronic interaction between the two metals of the dicobalt complex. The spectrum of (fv)[Rh(CO)2]2 also is very similar to the spectrum of CpRh(CO)2, except that the first metal ionizations in the bimetallic rhodium compound show a significant splitting (0.45 eV). This splitting is due to electronic interaction between the two metal centers which occurs via communication through the fulvalene π system. The differences in electronic structure are compared to the differences in electrochemical behavior of the Co and Rh fulvalene complexes.

KW - Bimetallic complexes

KW - Cobalt complexes

KW - Fulvalene complexes

KW - Gas phase photoelectron spectroscopy

KW - Rhodium complexes

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SN - 0020-1693

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SP - 623

EP - 629

JO - Inorganica Chimica Acta

JF - Inorganica Chimica Acta

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