Phosphine-substituted dithiolene complexes as ligands: communication between ruthenium(II) centers through a dimolybdenum bis(dithiolene) core.

Phosphine-substituted dithiolene complexes as ligands: communication between ruthenium(II) centers through a dimolybdenum bis(dithiolene) core. Research Abstract Details 

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Phosphine-substituted dithiolene complexes as ligands: communication between ruthenium(II) centers through a dimolybdenum bis(dithiolene) core. Abstract Text:

Harry Adams,Michael J Morris,Andrea E Riddiough,Lesley J Yellowlees,A B P Lever,Harry Adams,Michael J Morris,Andrea E Riddiough,Lesley J Yellowlees,A B P Lever,

The reaction of Mo2(SCH2CH2S)2Cp2 (1; Cp=eta-C5H5) with an excess of an alkyne in refluxing dichloromethane affords the bis(dithiolene) complexes Mo2(micro-SCR1=CR2S)2Cp2 (2a, R1=R2=CO2Me; 2b, R1=R2=Ph; 2c, R1=H, R2=CO2Me) whereas with 1 equiv of alkyne at room temperature the mixed dithiolene-dithiolate species Mo2(micro-SCR1=CR2S)(micro-SCH2CH2S)Cp2 (3a, R1=R2=CO2Me; 3b, R1=R2=Ph) are formed. The remaining dithiolate ligand in 3 can then be converted into a different dithiolene by reaction with a second alkyne. Applying this methodology, we have used bis(diphenylphosphino)acetylene to prepare the first examples of complexes containing phosphine-substituted dithiolene ligands: Mo2{micro-SC(CO2Me)=C(CO2Me)S}{micro-SC(PPh2)=C(PPh2)S}Cp2 (2g) and Mo2{micro-SC(PPh2)=C(PPh2)S}2Cp2 (2h). Tri- and tetrametallic complexes can then be assembled by coordination of these diphosphines to CpRuCl units by reaction with CpRu(PPh3)2Cl. Electrochemical studies of the Ru(II)/Ru(III) couple in Mo2{micro-SC(PPh2)=C(PPh2)S}2Cp2(RuClCp)2 (4b) reveals that the two separate ruthenium centers are oxidized electrochemically at different potentials, demonstrating communication between them through the dimolybdenum bis(dithiolene) core. Density functional theory calculations were carried out to explore the electronic structures of these species and to predict and assign their electronic spectra.

Phosphine-substituted dithiolene complexes as ligands: communication between ruthenium(II) centers through a dimolybdenum bis(dithiolene) core. Publishing Authors By Initials

H Adams,MJ Morris,AE Riddiough,LJ Yellowlees,AB Lever,H Adams,MJ Morris,AE Riddiough,LJ Yellowlees,AB Lever,

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Phosphine-substituted dithiolene complexes as ligands: communication between ruthenium(II) centers through a dimolybdenum bis(dithiolene) core. Journal Published:

PUBLICATION TYPE: Journal Article

Journal: Inorganic chemistry

VOLUME: 46

Page Numbers: 9790-807

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ISSN: 0020-1669

DAY: 2

MONTH: 10

YEAR: 2007

Phosphine-substituted dithiolene complexes as ligands: communication between ruthenium(II) centers through a dimolybdenum bis(dithiolene) core. Information

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LANGUAGE: eng

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AFFILIATION: Department of Chemistry, University of Sheffield, Sheffield S3 7HF, UK.

Country: United States

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MEDLINETA: Inorg Chem

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