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Mass spectrometry-directed synthesis of early–late sulfide-bridged heterobimetallic complexes from the metalloligand [Pt₂(PPh₃)₄(μ-S)₂] and oxo compounds of vanadium(V), molybdenum(VI) and uranium(VI)

Abstract
The metalloligand [Pt₂(PPh₃)₄(μ-S)₂] has been found to react with the transition metal oxo compounds, ammonium metavanadate, sodium molybdate, and the actinide complex uranyl nitrate to give sulfide-bridged heterobimetallic complexes [Pt₂(PPh₃)₄(μ₃-S)₂VO(OMe)₂]⁺, [Pt₂(PPh₃)₄(μ₃-S)₂MoO₂(OMe)]⁺, and [Pt₂(PPh₃)₄(μ₃-S)₂UO₂( ₂-NO₃)₂], respectively. Electrospray mass spectrometry (ESMS) was used to probe the reactivity of [Pt₂(PPh₃)₄(μ-S)₂] and thus identify likely targets for isolation and characterization. ESMS has also been used to investigate fragmentation pathways of the new species. No bimetallic species were detected with hydrated La(NO₃)₃or Th(NO₃)₄, or with the lanthanide shift reagent Eu(fod)₃ (fod = 6,6,7,7,8,8,8-heptafluoro-2,2-dimethyl-3,5-octanedionate). X-Ray crystal structure determinations have been carried out on [Pt₂(PPh₃)₄(μ₃-S)₂VO(OMe)₂]⁺, 2, (as its hexafluorophosphate salt) and [Pt₂(PPh₃)₄(μ₃-S)₂UO₂( ₂-NO₃)₂], 4. The vanadium atom of 2 has a distorted square pyramidal geometry, while the uranium in 4 has the expected linear dioxo coordination geometry, with two bidentate nitrates and a bidentate {Pt₂S₂} moiety.
Type
Journal Article
Type of thesis
Series
Citation
Fong, S. W. A., Yap, W. T., Vittal, J. J., Henderson, W., & Hor, T. S. A. (2002). Mass spectrometry-directed synthesis of early–late sulfide-bridged heterobimetallic complexes from the metalloligand [Pt₂(PPh₃)₄(μ-S)₂] and oxo compounds of vanadium(V), molybdenum(VI) and uranium(VI). Journal of Chemical Society Dalton Transactions, 1826-1831.
Date
2002
Publisher
Royal Society of Chemistry
Degree
Supervisors
Rights
This is an author’s accepted version of an article published in the Journal of Chemical Society Dalton Transactions. Used with permission.