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Fully delocalized (ethynyl)(vinyl)phenylene-bridged diruthenium radical complexes.

Abstract : Diruthenium complexes [(X)(dppe)2Ru-C≡C-1,4-C6H4-CH:CH-RuCl(CO)(PiPr3)2] (1a,b, X = = Cl, C≡CPh) contg. an unsym. (ethynyl)(vinyl)phenylene bridging ligand were prepd. by alkyne insertion into Ru-H-bond and compared to their sym. 1,4-bis(ethynyl)phenylene- and 1,4-divinylphenylene-bridged congeners and their mononuclear alkynyl precursors. Electrochem. and UV/vis/NIR, IR, and EPR spectroscopic studies on the neutral complexes and their various oxidized forms indicate bridging ligand-centered oxidn. processes and uniform charge and spin delocalization over both dislike organoruthenium moieties despite differences in their intrinsic redox potentials. Comparison between the chloro and the phenylacetylide-terminated derivs. 1a,b suggests further that the conjugated organometallic π-system extends over the entire unsatd. backbone including the terminal ligand at the alkynyl ruthenium site. This paves the way to even more extended π-conjugated organoruthenium arrays for long-range electronic interactions. [on SciFinder(R)]
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Submitted on : Thursday, February 23, 2017 - 6:07:29 PM
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Florian Pevny, Emmanuel Di Piazza, Lucie Norel, Malte Drescher, Rainer F. Winter, et al.. Fully delocalized (ethynyl)(vinyl)phenylene-bridged diruthenium radical complexes.. Organometallics, American Chemical Society, 2010, 29 (Copyright (C) 2017 American Chemical Society (ACS). All Rights Reserved.), pp.5912--5918. ⟨10.1021/om1007133⟩. ⟨hal-01475543⟩



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