Synthesis, structures and reactivity of bis(diphenylphosphino)-methane (dppm)-substituted selenido osmium carbonyl clusters

Addition of diphenyl diselenide (PhSeSePh) to the clusters [Os3(CO)10(μ-dppm)] and [(μ-H)Os3(CO)8{Ph2PCH2P(Ph)C6H4}]: X-ray structures of [Os2(CO)4(μ-SePh)2(μ-dppm)], [Os3(CO)6(μ-CO)(μ-Se)2(μ-C6H4)(μ-dppm)] and two isomers of [Os3(CO)8(μ-SePh)2(μ-dppm)]

“…(2) A}. The Os(1)-Os (2) bond distance of 2.7454 (12) A in 5 is comparable to the Os-Os distances found in the related dinuclear compounds [Os 2 (CO) 6 (l-1,2-S 2 C 6 H 4 )] {2.686 (2) A} [17] and [Os 2 (CO) 6 (l-SCH 2 CH 2 S)] {2.710 (1) A} [18] but is significantly shorter than that observed in [Os 2 (CO) 6 (l-Se)(l-dppm)] {2.8933 (2) A} [11]. The Os-Se-Os angles are highly acute with the values of 65.82(5)°and 64.82(5)°at Se (1) and Se (2).…”

“…On the other hand, there are only a few reports concerning the synthesis and reactivity of diphosphine substituted selenido triosmium carbonyl clusters. We have recently demonstrated the synthesis and reactivity of some dppm substituted triosmium clusters containing capping selenido ligand from the reactions of [Os 3 (CO) 10 (MeCN) 2 ] with dppmSe 2 and dppmSe through oxidative transfer of selenium atom from the dppm ligand to the zero-valent osmium atom [11]. Another approach to the synthesis of bridging selenido metal carbonyl clusters is the cleavage of Se-Se bond of diaryldiselenide [12][13][14].…”

“…Another approach to the synthesis of bridging selenido metal carbonyl clusters is the cleavage of Se-Se bond of diaryldiselenide [12][13][14]. For example, Lewis and coworkers [12] reported that the lightly stabilized cluster [Os 3 (CO) 11 (MeCN)] reacts with PhSeSePh at room temperature to give the 50-electron cluster [Os 3 (CO) 10 (l-SePh) 2 ] (3) by the cleavage of Se-Se bond of the diselenide. Deeming and coworkers [13,14] also investigated the reactions of [Os 3 (CO) 10 [Os 3 (CO) 10 (l-PhSe 2 Ph)] (1) with an intact Se-Se bond which readily forms [Os 3 (CO) 10 (l-SePh) 2 ] (2) by cleavage of the Se-Se bond of the ligand and then thermally isomerizes to 3 (Scheme 1).…”

“…The chemistry of the bridging dppm triosmium cluster [Os 3 (CO) 10 (l-dppm)] (4) and its orthometallated, unsaturated derivative [(l-H)Os 3 (CO) 8 {Ph 2 PCH 2 P(Ph) C 6 H 4 }] (11) has been studied by several groups [15] and continues to be the focus of considerable attention. The interest in these complexes is not only due to the special ability of the diphosphine ligand to maintain the metal cluster framework intact during chemical reactions but also because of the unsaturated character of 11 which allows it to react with various small inorganic and organic molecules under mild conditions to give many interesting and potentially useful compounds.…”

Cleavage of Ge–S and C–H bonds in the reaction of electron-deficient [Os3(CO)8(μ-H)(μ3-Ph2PCH2P(Ph)C6H4)] with Ph3GeSPh: Generation of thiophenol derivatives [Os3(CO)8(μ-H)(μ-SPh)(μ-dppm)] and [Os3(CO)7(μ-H)(μ-SPh)(μ3-SC6H4)(μ-dppm)]

“…[1][2][3][4][5][6][7][8][9][10][11][12][13][14][15] Electron-deficiency in 1 makes it more vulnerable to attack by nucleophiles and practically it reacts with a wide range of electron donor ligands under mild conditions relative to electron precise complexes. We also reported the Os-Sn compound [Os 3 (CO) 9 (µ-SPh)(µ 3-SnPh 2 )(NCMe)(η 1 -C 6 H 5 ) 2 ] from the reaction of [Os 3 (CO) 10 (NCMe) 2 ] with Ph 3 SnSPh.…”