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Type: Journal article
Title: Syntheses, structures and redox properties of some complexes containing the Os(dppe)Cp* fragment, including [{Os(dppe)Cp*}2(m-CºCCºC)]
Other Titles: Syntheses, structures and redox properties of some complexes containing the Os(dppe)Cp* fragment, including [{Os(dppe)Cp*}2(m-CoCCoC)]
Author: Bruce, M.
Costuas, K.
Davin, T.
Halet, J.
Kramarczuk, K.
Low, P.
Nicholson, B.
Perkins, G.
Roberts, R.
Skelton, B.
Smith, M.
White, A.
Citation: Dalton Transactions (Print Edition), 2007; 46(46):5387-5399
Publisher: Royal Soc Chemistry
Issue Date: 2007
ISSN: 1477-9226
Statement of
Michael I. Bruce, Karine Costuas, Thomas Davin, Jean-François Halet, Kathy A. Kramarczuk, Paul J. Low, Brian K. Nicholson, Gary J. Perkins, Rachel L. Roberts, Brian W. Skelton, Mark E. Smith and Allan H. White
Abstract: The sequential conversion of [OsBr(cod)Cp*] ( 9) to [OsBr(dppe)Cp*] ( 10), [Os(CCH2)(dppe)Cp*]PF6 ([ 11]PF6), [Os(CCH)(dppe)Cp*] ( 12), [{Os(dppe)Cp*}2{µ-(CCH–CHC)}][PF6]2 ([ 13](PF6)2) and finally [{Os(dppe)Cp*}2(µ-CCCC)] ( 14) has been used to make the third member of the triad [{M(dppe)Cp*}2(µ-CCCC)] (M = Fe, Ru, Os). The molecular structures of [ 11]PF6, 12 and 14, together with those of the related osmium complexes [Os(NCMe)(dppe)Cp*]PF6 ([ 15]PF6) and [Os(CCPh)(dppe)Cp*] ( 16), have been determined by single-crystal X-ray diffraction studies. Comparison of the redox properties of 14 with those of its iron and ruthenium congeners shows that the first oxidation potential E1 varies as: Fe Os < Ru. Whereas the Fe complex has been shown to undergo three sequential 1-electron oxidation processes within conventional electrochemical solvent windows, the Ru and Os compounds undergo no fewer than four sequential oxidation events giving rise to a five-membered series of redox related complexes [{M(dppe)Cp*}2(µ-C4)]n+ (n = 0, 1, 2, 3 and 4), the osmium derivatives being obtained at considerably lower potentials than the ruthenium analogues. These results are complimented by DFT and DT DFT calculations.
Rights: Copyright © 2007 Royal Society of Chemistry
RMID: 0020073728
DOI: 10.1039/b712104k
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Appears in Collections:Chemistry and Physics publications

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