Synthesis of new thiol derivatives of [Os3(CO)12]; crystal structure of [Os3(CO)10(μ-H){μ-SC)(CH3)3}]

Detection of a novel intermediate in the addition of thiols to osmium carbonyl clusters

“…The high-field resonance may be ascribed to the bridging hydride of the final product 3 † by comparison to previously known [Os 3 (m-H)(CO) 10 (m-SR)] clusters. 4,5 The shift of the second resonance occurs at lower field than may be expected for a hydride coordinated to a triosmium cluster; 6 the signal is assigned to the thiol hydrogen and it is suggested that the shift arises from an agostic interaction of this hydrogen with one of the osmium atoms. The T 1 relaxation times for the two signals are similar, although not identical, being 2.08 s for the intermediate 2 and 4.37 s for the final species 3.…”

“…3 We are currently studying whether it is possible to monitor the initial coordination of thiols to polynuclear metal complexes and to relate these phenomena to HDS processes. 4 Here we wish to describe how the reaction between [Os 3 (CO) 2) is proposed to contain an agostic Os-H-S interaction; to our knowledge, this is the first example of an agostic interaction involving a thiol hydrogen. Two resonances could be detected at high field when the reaction of stoichiometric equivalents of 1 and para-thiocresol was monitored by 1 H NMR at ambient temperature.…”

Hydrido-sulfido-bridged triangular Os3cluster compounds with different phosphine ligand substitution patterns

“…Related unsubstituted Os 3 carbonyl compounds exhibit almost equal bond lengths for all three OsÐOs edges, e.g. Os 3 ("-H)["-SC(H)N-p-C 6 H 4 F]-(CO) 10 (Adams & Dawoodi, 1981) with a bond difference, Á, of 0.003 A Ê , Os 3 ("-H)("-SC NCH 2 CH 2 S)(CO) 10 (Á = 0.002 A Ê ; Brodie et al, 1983), Os 3 ("-H)["-SC(CH 3 ) 3 ](CO) 10 (Á = 0.004 A Ê ; Monari et al, 1996), and Os 3 ("-H)-["-SC(HPh 2 )](CO) 10 (Á = 0.008 A Ê ; Holden et al, 1983).…”