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Phosphane effects on formation and reactivity of [Ru(L)(PR3)(`N2Me2S2')] complexes with L=N2, N2H4, NH3, and CO by D. Sellmann; A. Hille; A. Rösler; F.W. Heinemann; M. Moll is a Chemistry article available to read on EtoBox.

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Metal-sulfur complex fragments, to which small molecules like N 2 , N 2 H 2 , N 2 H 4 , NH 3 , or CO can bind, are desirable model compounds concerning enzymatic N 2 fixation. This paper reports on the effects of the phosphane co-ligand on formation and reactivity of [ with nitrogenase relevant ligands, especially N 2 , N 2 H 4 , NH 3 , and CO. Treatment of [Ru(NCCH 3 ) 4 Cl 2 ] with Li 2 'N 2 Me 2 S 2 ', excessive LiOMe, bulky PPh 3 or PCy 3 , respectively, led to the formation of two series of [Ru While the use of PPh 3 (h 1⁄4 145°) yielded cis,trans and cis,cis isomers of [Ru(NCCH 3 )(PPh 3 )('N 2 Me 2 S 2 ')] (1b, 1c), no isomer formation was observed with the bulkier phosphane PCy 3 (h 1⁄4 170°). Sterically less demanding phosphanes (h 1⁄4 118-132°) afforded bisphosphane complexes [Ru(PR 3 ) 2 ('N 2 Me 2 S 2 ')] [2d (R 1⁄4 Me), 2e (R 1⁄4 Et), 2f (R 1⁄4 nPr), and 2g (R 1⁄4 nBu)], which were practically inert and could only be converted in two cases and under drastic reaction conditions into the CO complexes [Ru(CO)(PR 3 )('N 2 Me 2 S 2 ')] [4e (R 1⁄4 Et), 4f (R 1⁄4 nPr)]. The chelating bidentate phosphane dppe (bisdiphenylphosphanoethane) yielded exclusively the mononuclear com

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Author

D. Sellmann; A. Hille; A. Rösler; F.W. Heinemann; M. Moll

Publisher

Elsevier Science; Elsevier ; Elsevier BV (ISSN 0020-1693)

Published

2004

Language

EN

Field

Chemistry (Physical Sciences)