Acetylenedithiolate as directional bridging ligand in cobalt(I) alkyne platinum dithiolato bimetallic complexes

作者：Seidel Wolfram W^*; Meel Matthias J; Hupka Florian; Weigand Jan J

来源：Dalton Transactions, 2010, 39(2): 624-631.

DOI：10.1039/b913859e

The eta(2)-C,C'-acetylenedithiolate (acdt(2-)) complex K[(triphos)Co(acdt)], K-5, {triphos = 1,1,1-tris(diphenylphosphinomethyl)ethane} was obtained by consecutive removal of S-protection groups in [(triphos)Co(1)]PF(6), 3-PF(6) (1 = 1-Trimethylsilyl-7-phenyl-3,6-dithiahept-4-ine). Reaction of K-5 with selected Pt(II) salts resulted in the formation of the new heterobimetallic complexes [(phen)Pt(5)]BPh(4), 6-BPh(4), (phen = 1,10-phenanthroline) and [(dppe)Pt(5)]BPh(4), 7-BPh(4), {dppe = 1,2-bis(diphenylphosphino)ethane}, which were fully characterized. X-ray diffraction studies showed that Co and Pt are linked by acdt(2-) in the eta(2)-C,C'-kappa(2)-S,S'-bridging mode. The electronic structure of 6-BPh(4) and 7-BPh(4) was investigated by electronic absorption spectroscopy, cyclic voltammetry and X-band EPR spectroscopy of neutral 7. In addition, NMR spectroscopy, X-ray diffraction and reactivity studies with the alkyne complexes [(PMe(3))(3)Co(1)]-PF(6), 2-PF(6), with 3-PF(6) and the intermediate product [(triphos)Co{eta(2)-(S)C(2)(SCH(2)Ph)}], 4, uncovered the flexibility of the CoC(2)S(2)-moiety within the persisting complex scaffold throughout the synthetic scheme.

• 出版日期2010