Di-μ-iodo-1κ:2κl-tris(tri-m-tolylphosphine) -1κ2 P,P′:2κP″-dicopper(I): A new polymorph

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Reactions of [(mu-H)Os-3(CO)(10)(mu-OMe)] and [(mu-H)Os-3(CO)9(mu-OMe)(MeCN)] with dppm, dppe, dppp, and PPh2H: X-ray crystal structures of [(mu-H)Os-3(CO)8(mu-OMe)-(mu(2)-eta(2)-dppm)] and [(mu-H)Os-3(CO)(9)(mu-OMe)(PPh2H)]

Treatment of [(mu-H)Os-3(CO)(10)(mu-OMe)] (1) with dppm {dppm = bis(diphenylphosphino)methane} at 110 degrees C gave the known compound [Os-3(CO)(10)(mu(2)-eta(2)-dppm)] (2) and the new compound [(mu-H)Os-3(CO)(8)(mu-OMe)(mu(2)-eta(2)-dppm)] (3). A similar reaction of 1 with dppe {dppe=bis(diphenylphosphino)ethane} afforded two products, [(mu-H)Os-3(CO)(8)(mu-OMe)(mu(1)-eta(2)-dppe)] (5) and [(mu-H)Os-3(CO)(8)(mu-OMe)(mu(2)-eta(2)-dppe)] (6) which differ in the mode of bonding of the dppe ligand. The reaction of 1 with dppp {dppp = bis(diphenylphosphino)propane} at 110 degrees C gave exclusively [(mu-H)Os-3(CO)(8)(mu-OMe)(mu(2)-eta(2)-dppp)] (7) which exists as two isomers in solution. Compounds 2, 3, and 5-7 are also obtained in almost similar yields from reactions of [(mu-H)Os-3(CO)(8)(mu-OMe)(MeCN)] (4) with the appropriate diphosphine at ambient temperature. The reaction of 1 with PPh2H at 110 degrees C gave the new compounds [(mu-H)Os-3(CO)(9)(mu-OMe)(PPh2H)] (8) and [(mu-H)Os-3(CO)(7)(mu-PPh2)(2)(PPh2H)](10) and the previously reported compound [(mu-H)Os-3(CO)(8)(mu-OMe)(PPh2H)] (9). The molecular structures of 3 and 8 were determined by single crystal X-ray diffraction. In compound 3, the dppm ligand bridges the same Os-Os edge as the hydride and the methoxide ligand. In 8, the PPhH ligand occupies a 'pseudo' axial site on one of the osmium atoms bearing the bridging hydride and methoxide ligand

Triphenylphosphine-substituted selenido and sulfido clusters of osmium derived from Ph3P=Se or Ph3P=S

Cleavage of P=Se bonds occurs readily in the room-temperature treatment of [Os-3(CO) (10)(MeCN)(2)] with Ph3P=Se to give three new compounds, [Os-3(mu(3)-Se)(2)(CO)(8)(PPh3)] (2), [Os-3(mu(3)-Se)( mu(3)-CO)(CO)(7)(PPh3)(2)] (5) and [Os3(mu-OH)(2)(CO)(8)(PPh3)(2)] (6), respectively, and three known compounds, [Os-3(mu(3)-Se)(2)(CO)(9)] (1), [Os-3(mu(3)-Se)(mu-CO)(2)(CO)(7)(PPh3)] (3), and 1,2-[Os-3(CO)(10)(PPh3)(2)] (4). No evidence for any product containing a co-ordinated Ph3P--Se ligand was obtained. The analogous reaction between [OS3(CO)10(MeCN)2] and Ph3P=S produces five new compounds [Os-3(mu(3)-S)(2)(CO)(8)(PPh3)] (7), [Os-3(mu(3)-S)(mu-CO)(2)(CO)(7)(PPh3)] (8), [Os-3(mu(3)-S) (mu(3)- CO)(CO)(7)(PPh3)(2)] (9), [Os-3(mu(3)-)(2)(CO)(7)(PPh3)(2)] (11) and compound 6 in addition to the known compound 4. Treatment of with Me3NO at 50 degrees C gives the trinuclear cluster [Os-3(mu(3)-Se)(2)(CO)(7)(PPh3)(NMe3)] (13) and the hexanuclear cluster [Os-6(mu(3)-Se)(4)(CO)(14) (PPh3)(2)] (12). Treatment of compound 1 with PPh3 and Me3NO at room temperature gives [Os-3(mu(3)-Se)(2)(CO)(7)(PPh3)(2)] (10). Compound 2 reacts with PPh3 similarly to give 10. Compound 3 reacts with elemental selenium at 110 degrees C to give 2. The new compounds 2, 5, 6 and 8 were characterized by single-crystal X-ray diffraction. The compounds 3, 5, 8 and 9 contain Os-3(mu(3)-S) or Os-3(mu(3)-Se)cluster cores with three metal-metal bonds while 2, 7, 10, 11 and 12 contain Os-3(mu(3)-S)(2) or Os(mu(3)-Se)(2) cores two metal-metal bonds. The two hydroxy ligands in the triosmium cluster 6 bridging the open osmium-osmium edge and are probably derived from water. A study of the dynamic exchange of PPh3 ligands in 5 is also reported