Infrared spectroelectrochemistry of [Rh(TM4)4M(CO)5]22+ (TM4=2,5-diisocyano-2,5-dimethylhexane; M=Re, Mn): electrontransfer-promoted metal-metal bond cleavage and formation

Michael G. Hill; John P. Bullock; Timothy Wilson; Paul Bacon; Christine A. Blaine; Kent R. Mann

doi:10.1016/0020-1693(94)04071-0

Infrared spectroelectrochemistry of [Rh(TM4)₄M(CO)₅]₂²⁺ (TM4=2,5-diisocyano-2,5-dimethylhexane; M=Re, Mn): electrontransfer-promoted metal-metal bond cleavage and formation

Michael G. Hill, John P. Bullock, Timothy Wilson, Paul Bacon, Christine A. Blaine, Kent R. Mann

Chemistry (Twin Cities)

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

15 Scopus citations

Abstract

Two tetranuclear complexes of the form Rh₂(TM4)₄(M(CO)₅)₂²⁺ (TM4=2,5-diisocyano-2,5-dimethylhexane; M=Mn or Re) have been studied by electrochemical (CV) and IR spectroelectrochemical methods. In 0.1 M TBA⁺PF₆^-/CH₃CN (TBA⁺= tetrabutylammonium), 1e^- oxidation of Rh₂(TM4)₄(Re(CO)₅)₂²⁺ produces a stable radical (Rh₂(TM4)₄(Re(CO)₅)₂³⁺) that has been characterized by EPR and IR spectroscopy. Upon further oxidation, one RhRe bond is cleaved, resulting in the formation of Rh₂(TM4)₄(Re(CO)₅)³⁺ and Re(CO)₅(CH₃CN)⁺. The trimetallic fragment Rh₂(TM4)₄(Re(CO)₅)³⁺ is reduced by a net 2e^- process to yield free Rh₂(TM4)₄²⁺ and Re(CO)₅^-. These successive 2e^-oxidation/reduction reactions of Rh₂(TM4)₄(Re(CO)₅)₂²⁺ ultimately yield a solution containing Rh₂(TM4)₄²⁺, Re(CO)₅(CH₃CN)⁺ and Re(CO)₅^-. For Rh₂(TM4)₄(Mn(CO)₅)₂²⁺, oxidation occurs via a net 2e^- process to form the tetranuclear tetracation, Rh₂(TM4)₄(Mn(CO)₅)₂⁴⁺ Further oxidation of this species results in RhMn bond cleavage, giving Rh₂(TM4)₄⁴⁺ and two equivalents of Mn(CO)₅(CH₃CN)⁺. The initially formed, 1e^-- oxidized radical, Rh₂(TM4)₄(Mn(CO)₅)₂³⁺, has been observed transiently via fast-scan cyclic voltammetry. These ET-induced bond cleavage reactions are paralleled in the reduction chemistry of Rh₂(TM4)₄(Mn(CO)₅)₂²⁺ and Rh₂(TM4)₄(Re(CO)₅)₂²⁺. Reduction of both complexes occurs by a net 2e^- process, yielding free Rh₂(TM4)₄²⁺ and M(CO)₅^-. Interestingly, upon oxidation at the coupled return for this irreversible process, the tetranuclear starting materials are regenerated in quantitative yield (i.e. no M₂(CO)₁₀ is produced). This chemistry stands in sharp contrast to the oxidations of M(CO)₅^- anions, which produce M₂(CO)₁₀ in the absence of Rh₂(TM4)₄²⁺. We suggest that oxidation of Rh₂(TM4)₄²⁺, M(CO)₅^- tight ion aggregates produce M(CO)₅ radicals that are entirely scavenged by Rh₂(TM4)₄²⁺ to form the tetranuclear species.

Original language	English (US)
Pages (from-to)	61-68
Number of pages	8
Journal	Inorganica Chimica Acta
Volume	226
Issue number	1-2
DOIs	https://doi.org/10.1016/0020-1693(94)04071-0
State	Published - Nov 1994

Bibliographical note

Funding Information:
We thank Dr Sam Kim at the Jet Propulsion Laboratory for the use of his EPR spectrometer. M.G.H. acknowledges the University of Minnesota graduate school for a Stanwood Johnston Memorial Fellowship. P.B. acknowledges the Lando-SOHIO foundation for an undergraduate research fellowship. This research was supported in part through a grant from the National Science Foundation.

Keywords

Electron transfer
Isocyanide complexes
Rhodium complexes
Spectroelectrochemistry

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10.1016/0020-1693(94)04071-0

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@article{5518ebba07e54d43877a4b651936a795,

title = "Infrared spectroelectrochemistry of [Rh(TM4)4M(CO)5]22+ (TM4=2,5-diisocyano-2,5-dimethylhexane; M=Re, Mn): electrontransfer-promoted metal-metal bond cleavage and formation",

abstract = "Two tetranuclear complexes of the form Rh2(TM4)4(M(CO)5)22+ (TM4=2,5-diisocyano-2,5-dimethylhexane; M=Mn or Re) have been studied by electrochemical (CV) and IR spectroelectrochemical methods. In 0.1 M TBA+PF6-/CH3CN (TBA+= tetrabutylammonium), 1e- oxidation of Rh2(TM4)4(Re(CO)5)22+ produces a stable radical (Rh2(TM4)4(Re(CO)5)23+) that has been characterized by EPR and IR spectroscopy. Upon further oxidation, one RhRe bond is cleaved, resulting in the formation of Rh2(TM4)4(Re(CO)5)3+ and Re(CO)5(CH3CN)+. The trimetallic fragment Rh2(TM4)4(Re(CO)5)3+ is reduced by a net 2e- process to yield free Rh2(TM4)42+ and Re(CO)5-. These successive 2e-oxidation/reduction reactions of Rh2(TM4)4(Re(CO)5)22+ ultimately yield a solution containing Rh2(TM4)42+, Re(CO)5(CH3CN)+ and Re(CO)5-. For Rh2(TM4)4(Mn(CO)5)22+, oxidation occurs via a net 2e- process to form the tetranuclear tetracation, Rh2(TM4)4(Mn(CO)5)24+ Further oxidation of this species results in RhMn bond cleavage, giving Rh2(TM4)44+ and two equivalents of Mn(CO)5(CH3CN)+. The initially formed, 1e-- oxidized radical, Rh2(TM4)4(Mn(CO)5)23+, has been observed transiently via fast-scan cyclic voltammetry. These ET-induced bond cleavage reactions are paralleled in the reduction chemistry of Rh2(TM4)4(Mn(CO)5)22+ and Rh2(TM4)4(Re(CO)5)22+. Reduction of both complexes occurs by a net 2e- process, yielding free Rh2(TM4)42+ and M(CO)5-. Interestingly, upon oxidation at the coupled return for this irreversible process, the tetranuclear starting materials are regenerated in quantitative yield (i.e. no M2(CO)10 is produced). This chemistry stands in sharp contrast to the oxidations of M(CO)5- anions, which produce M2(CO)10 in the absence of Rh2(TM4)42+. We suggest that oxidation of Rh2(TM4)42+, M(CO)5- tight ion aggregates produce M(CO)5 radicals that are entirely scavenged by Rh2(TM4)42+ to form the tetranuclear species.",

keywords = "Electron transfer, Isocyanide complexes, Rhodium complexes, Spectroelectrochemistry",

author = "Hill, {Michael G.} and Bullock, {John P.} and Timothy Wilson and Paul Bacon and Blaine, {Christine A.} and Mann, {Kent R.}",

note = "Funding Information: We thank Dr Sam Kim at the Jet Propulsion Laboratory for the use of his EPR spectrometer. M.G.H. acknowledges the University of Minnesota graduate school for a Stanwood Johnston Memorial Fellowship. P.B. acknowledges the Lando-SOHIO foundation for an undergraduate research fellowship. This research was supported in part through a grant from the National Science Foundation.",

year = "1994",

month = nov,

doi = "10.1016/0020-1693(94)04071-0",

language = "English (US)",

volume = "226",

pages = "61--68",

journal = "Inorganica Chimica Acta",

issn = "0020-1693",

publisher = "Elsevier BV",

number = "1-2",

}

TY - JOUR

T1 - Infrared spectroelectrochemistry of [Rh(TM4)4M(CO)5]22+ (TM4=2,5-diisocyano-2,5-dimethylhexane; M=Re, Mn)

T2 - electrontransfer-promoted metal-metal bond cleavage and formation

AU - Hill, Michael G.

AU - Bullock, John P.

AU - Wilson, Timothy

AU - Bacon, Paul

AU - Blaine, Christine A.

AU - Mann, Kent R.

N1 - Funding Information: We thank Dr Sam Kim at the Jet Propulsion Laboratory for the use of his EPR spectrometer. M.G.H. acknowledges the University of Minnesota graduate school for a Stanwood Johnston Memorial Fellowship. P.B. acknowledges the Lando-SOHIO foundation for an undergraduate research fellowship. This research was supported in part through a grant from the National Science Foundation.

PY - 1994/11

Y1 - 1994/11

N2 - Two tetranuclear complexes of the form Rh2(TM4)4(M(CO)5)22+ (TM4=2,5-diisocyano-2,5-dimethylhexane; M=Mn or Re) have been studied by electrochemical (CV) and IR spectroelectrochemical methods. In 0.1 M TBA+PF6-/CH3CN (TBA+= tetrabutylammonium), 1e- oxidation of Rh2(TM4)4(Re(CO)5)22+ produces a stable radical (Rh2(TM4)4(Re(CO)5)23+) that has been characterized by EPR and IR spectroscopy. Upon further oxidation, one RhRe bond is cleaved, resulting in the formation of Rh2(TM4)4(Re(CO)5)3+ and Re(CO)5(CH3CN)+. The trimetallic fragment Rh2(TM4)4(Re(CO)5)3+ is reduced by a net 2e- process to yield free Rh2(TM4)42+ and Re(CO)5-. These successive 2e-oxidation/reduction reactions of Rh2(TM4)4(Re(CO)5)22+ ultimately yield a solution containing Rh2(TM4)42+, Re(CO)5(CH3CN)+ and Re(CO)5-. For Rh2(TM4)4(Mn(CO)5)22+, oxidation occurs via a net 2e- process to form the tetranuclear tetracation, Rh2(TM4)4(Mn(CO)5)24+ Further oxidation of this species results in RhMn bond cleavage, giving Rh2(TM4)44+ and two equivalents of Mn(CO)5(CH3CN)+. The initially formed, 1e-- oxidized radical, Rh2(TM4)4(Mn(CO)5)23+, has been observed transiently via fast-scan cyclic voltammetry. These ET-induced bond cleavage reactions are paralleled in the reduction chemistry of Rh2(TM4)4(Mn(CO)5)22+ and Rh2(TM4)4(Re(CO)5)22+. Reduction of both complexes occurs by a net 2e- process, yielding free Rh2(TM4)42+ and M(CO)5-. Interestingly, upon oxidation at the coupled return for this irreversible process, the tetranuclear starting materials are regenerated in quantitative yield (i.e. no M2(CO)10 is produced). This chemistry stands in sharp contrast to the oxidations of M(CO)5- anions, which produce M2(CO)10 in the absence of Rh2(TM4)42+. We suggest that oxidation of Rh2(TM4)42+, M(CO)5- tight ion aggregates produce M(CO)5 radicals that are entirely scavenged by Rh2(TM4)42+ to form the tetranuclear species.

AB - Two tetranuclear complexes of the form Rh2(TM4)4(M(CO)5)22+ (TM4=2,5-diisocyano-2,5-dimethylhexane; M=Mn or Re) have been studied by electrochemical (CV) and IR spectroelectrochemical methods. In 0.1 M TBA+PF6-/CH3CN (TBA+= tetrabutylammonium), 1e- oxidation of Rh2(TM4)4(Re(CO)5)22+ produces a stable radical (Rh2(TM4)4(Re(CO)5)23+) that has been characterized by EPR and IR spectroscopy. Upon further oxidation, one RhRe bond is cleaved, resulting in the formation of Rh2(TM4)4(Re(CO)5)3+ and Re(CO)5(CH3CN)+. The trimetallic fragment Rh2(TM4)4(Re(CO)5)3+ is reduced by a net 2e- process to yield free Rh2(TM4)42+ and Re(CO)5-. These successive 2e-oxidation/reduction reactions of Rh2(TM4)4(Re(CO)5)22+ ultimately yield a solution containing Rh2(TM4)42+, Re(CO)5(CH3CN)+ and Re(CO)5-. For Rh2(TM4)4(Mn(CO)5)22+, oxidation occurs via a net 2e- process to form the tetranuclear tetracation, Rh2(TM4)4(Mn(CO)5)24+ Further oxidation of this species results in RhMn bond cleavage, giving Rh2(TM4)44+ and two equivalents of Mn(CO)5(CH3CN)+. The initially formed, 1e-- oxidized radical, Rh2(TM4)4(Mn(CO)5)23+, has been observed transiently via fast-scan cyclic voltammetry. These ET-induced bond cleavage reactions are paralleled in the reduction chemistry of Rh2(TM4)4(Mn(CO)5)22+ and Rh2(TM4)4(Re(CO)5)22+. Reduction of both complexes occurs by a net 2e- process, yielding free Rh2(TM4)42+ and M(CO)5-. Interestingly, upon oxidation at the coupled return for this irreversible process, the tetranuclear starting materials are regenerated in quantitative yield (i.e. no M2(CO)10 is produced). This chemistry stands in sharp contrast to the oxidations of M(CO)5- anions, which produce M2(CO)10 in the absence of Rh2(TM4)42+. We suggest that oxidation of Rh2(TM4)42+, M(CO)5- tight ion aggregates produce M(CO)5 radicals that are entirely scavenged by Rh2(TM4)42+ to form the tetranuclear species.

KW - Electron transfer

KW - Isocyanide complexes

KW - Rhodium complexes

KW - Spectroelectrochemistry

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