Reaction of the unsaturated triosmium clusters [Os₃H(CO)₈{Ph₂PCH₂P(Ph)C₆H₄}] and [Os₃H(CO)₈{Ph₂PC(CH₂)P(Ph)C₆H₄}] with phosphines and phosphites; crystal structures of [Os₃H(CO)₈{Ph₂PCH₂P(Ph)C₆H₄}(PPrⁱ₃)], [Os₃(CO)₈(Ph₂PCH₂PPh₂){P(OMe)

Synthesis, structure and reactivity of triosmium clusters derived from the reactions of [Os3(CO)10(μ-dppm)] (dppm = Ph2PCH2PPh2) and [Os3(μ-H)(CO)8{Ph2PCH2P(Ph)C6H4}] with PHPh2

“…The synthesis and reactivity of triosmium clusters containing bridging diphosphine ligands [Os 3 (CO) 10 {µ-Ph 2 P(CH 2 ) n PPh 2 }] (n = 1-5) have widely been studied during the last decade. [1][2][3][4][5][6][7][8][9][10][11][12][13][14] In particular, the dppm [= bis(diphenylphosphino)methane, Ph 2 PCH 2 PPh 2 ] compound [Os 3 (CO) 10 (µ-dppm)] 1 has attracted considerable attention because of its novel reactivity to give many interesting species and also because of the special ability of dppm to maintain the metal cluster framework intact during chemical reactions. [3][4][5][6][7][8][9][10][11][12][13][14] For example, decarbonylation of 1 in refluxing toluene gives the co-ordinatively unsaturated cluster [Os 3 (µ-H)(CO) 8 {Ph 2 PCH 2 P(Ph)C 6 H 4 }] 2 which reacts with CO to form [Os 3 (µ-H)(CO) 9 {Ph 2 PCH 2 (Ph)C 6 H 4 }], 7 with H 2 to form [Os 3 (µ-H) 2 (CO) 8 (µ-dppm)], 8 with diphenylacetylene to form [Os 3 (CO) 8 (µ-dppm)(PhC᎐ ᎐ ᎐ CPh)] 9 and with [Au(PPh 3 )]PF 6 and HBF 4 to form the cationic clusters [Os 3 (µ-H)(CO) 8 {Ph 2 PCH 2 -P(Ph)C 6 H 4 }(µ-AuPPh 3 )]PF 6 and [Os 3 (µ-H) 2 (CO) 8 {Ph 2 PCH 2 -P(Ph)C 6 H 4 }]BF 4 respectively.…”

“…[1][2][3][4][5][6][7][8][9][10][11][12][13][14] In particular, the dppm [= bis(diphenylphosphino)methane, Ph 2 PCH 2 PPh 2 ] compound [Os 3 (CO) 10 (µ-dppm)] 1 has attracted considerable attention because of its novel reactivity to give many interesting species and also because of the special ability of dppm to maintain the metal cluster framework intact during chemical reactions. [3][4][5][6][7][8][9][10][11][12][13][14] For example, decarbonylation of 1 in refluxing toluene gives the co-ordinatively unsaturated cluster [Os 3 (µ-H)(CO) 8 {Ph 2 PCH 2 P(Ph)C 6 H 4 }] 2 which reacts with CO to form [Os 3 (µ-H)(CO) 9 {Ph 2 PCH 2 (Ph)C 6 H 4 }], 7 with H 2 to form [Os 3 (µ-H) 2 (CO) 8 (µ-dppm)], 8 with diphenylacetylene to form [Os 3 (CO) 8 (µ-dppm)(PhC᎐ ᎐ ᎐ CPh)] 9 and with [Au(PPh 3 )]PF 6 and HBF 4 to form the cationic clusters [Os 3 (µ-H)(CO) 8 {Ph 2 PCH 2 -P(Ph)C 6 H 4 }(µ-AuPPh 3 )]PF 6 and [Os 3 (µ-H) 2 (CO) 8 {Ph 2 PCH 2 -P(Ph)C 6 H 4 }]BF 4 respectively. 10 Another aspect of the reactivity of compound 1 or its acetonitrile derivative [Os 3 (CO) 9 (µ-dppm)(MeCN)] is the derivative chemistry with monodentate phosphines L to give [Os 3 (CO) 9 (µ-dppm)L] [L = PPh 3 , P(OMe) 3 or Ph 2 PCH 2 CH 2 -Si(OEt) 3 ] and with bidentate dppm to give [Os 3 (CO) 9 (µdppm)(dppm-P)] and [Os 3 (CO) 8 (µ-dppm) 2 ].…”

Reactions of the unsaturated triosmium cluster [(μ-H)Os3(CO)8(Ph2PCH2P(Ph)C6H4)] with HX (X=Cl, Br, F, CF3CO2,CH3CO2): X-ray structures of [(μ-H)Os3(CO)7(η1-Cl)(μ-Cl)2(μ-dppm)],[(μ-H)2Os3(CO)8(Ph2PCH2P(Ph)C6H4)]+[CF3O]− and the two isomers of [(μ-H)Os3(CO)8(μ-Cl)(μ-dppm)]

“…The reactions of the coordinatively unsaturated triosmium cluster [(l-H)Os 3 (CO) 8 (l 3 -g 3 -Ph 2 PCH 2 P(Ph)-C 6 H 4 )] (1) with a wide variety of small inorganic and organic ligands such as CO [15], H 2 [16], PR 3 [17], P(OR) 3 [20], EtSH [21], CH 3 CH(CH 3 )SH [21], PhSH [21], pySH [22], HSCH 2 CH 2 SH [23], HSCH 2 CH 2 -CH 2 SH [23], and Se [24] that afford many interesting and potentially useful compounds have been investigated. Our recent studies of the reactivity of 1 toward CH 2 CN 2 [25] and silanes [26] have uncovered some examples of its distinctly different reactivity patterns compared with unsaturated benzoheterocyclic triosmium clusters [27].…”

Rhodium Complexes ContainingO-Bonded NHxMe2−xCHO (x=0, 1, 2): X-Ray Structure of [Rh(PPh3)3(OCHNHMe)]ClO4

“…The weighting scheme w 1/s 2 (F) gave satisfactory agreement analyses. Programs, computers, and sources of scattering factor data have been described previously [21]. Crystallographic data are summarised in Table 1, and selected bond lengths and angles are collected in Table 2.…”