The protonation and hydrogen transfer processes in alkene and alkyne derivatives of Os3 and H2Os3(CO)10

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)]

“…Important bond lengths and angles of this anion are listed in Table 5. The average C-O and C-F distances (1.277(13) and 1.45(10) Å , respectively) and O-C-F and F-C-F angles (1.133 (8) and 104.86°, respectively) are comparable to those reported previously [32]. This anion is most likely formed by the stepwise fluorination and hydrolysis (by trace moisture) of CH 2 Cl 2 .…”

“…The reactions of triosmium carbonyl clusters with protic acids have been thoroughly investigated and found to exhibit a range of reactivity patterns [1][2][3][4][5][6][7][8]. Most common is simple protonation to give cationic hydrido species in which the hydride adopts a bridging coordination site [1][2][3][4][5] although cleavage of a metalcarbon [6] or a metal-metal bond [7] are known to occur as well.…”

“…For example, the parent compound [Os 3 (CO) 12 ] reacts with concentrated H 2 SO 4 to give the cationic species [(l-H)Os 3 (CO) 12 ] + [1]. The protonation of electron rich mono-and diphosphine derivatives occur more readily on treatment with weaker acids such as CF 3 CO 2 H. The unsaturated cluster [(l-H) 2 Os 3 (CO) 10 ] and its tertiary phosphine substituted derivatives [(l-H) 2 Os 3 (CO) 9 (L)] (L = PEt 3 , or PPh 3 ) react with CF 3 CO 2 H to give the cationic clusters [(l-H) 3 Os 3 (CO) 10 ] + and [(l-H) 3 Os 3 (CO) 9 L] + , respectively [8]. The cyclometallated compound [(l-H) 2 Os 3 (CO) 9 -(l 3 -P(C 6 H 4 )Ph)] reacts with Brønsted acids HX via a protonation followed by anion coordination to give the addition products [(l-H) 2 Os 3 (X)(CO) 9 (l-PPh 2 )] (X = F, Cl, Br or CF 3 CO 2 ) but with HBF 4 only the protonated complex [(l-H) 3 Os 3 (CO) 9 (l 3 -P(C 6 H 4 )Ph)] + is obtained [9].…”

“…quite acute {73.82(8)°} and is significantly smaller than the Os(2)-Cl(2)-Os(1) angle (106.99(10)°), but similar to the corresponding angle in [(l-H)Os 3 -(CO) 10 (l-Cl)] (70.83(9)°)[28]. The Os-P distances (2.307(3) and 2.334(3) Å ) are similar to those in 2.…”

47-Electron Organometallic Clusters Derived by Chemical and Electrochemical Oxidation of Trihydrido(alkylidyne)triruthenium and -triosmium Clusters. Ligand Additivity in Metal Clusters

“…The major cluster products are starting material and a diamagnetic material which we propose to be [H 3 Ru 3 (CO) 7 (PPh 3 ) 3 ] 1+ , a new 46-electron cluster. Although no Ru clusters of this or related compositions had been previously reported, the Os analogues [H 3 Os 3 (CO) 10 - n L n ] 1+ (L = PPh 3 ; n = 0, 1) have been prepared by protonation of unsaturated H 2 Os 3 (CO) 10 - n L n …”