88129-95-7Relevant academic research and scientific papers
Stepwise Reductive Acidolysis of OsH4(PMe2Ph)3. Mechanism of Hydrogen Elimination/Ligand Addition
Bruno, Joseph W.,Huffman, John C.,Caulton, Kenneth G.
, p. 1663 - 1669 (1984)
The polyhydride OsH4(PMe2Ph)3 (1) reacts with either HBF4.OEt2 or Ph3CPF6 and CH3CN to give X2 (6) (X=BF4, PF6).The acidolysis reaction proceeds in stepwise fashion through several intermediate species.Using limiting reagent quantities (acid and CH3CN), it is possible to either isolate or spectrally characterize OsH5(PMe2Ph)3+ (2), OsH3(PMe2Ph)3(CH3CN)+ (3), mer,cis-OsH(PMe2Ph)3(CH3CN)2+ (4), and mer-Os(PMe2Ph)3(CH3CN)32+ (5) on the pathway to 6.Additionally, kinetic and labeling studies indicate that H2 substitution by CH3CN occurs via a preequilibrium H2 loss and subsequent trapping by CH3CN.The X-ray diffraction structure of 6 (X=PF6) is also reported.
Solvento complexes of tungsten, rhenium, osmium, and iridium and the X-ray crystal structure of [IrH2(Me2CO)2(PPh3) 2]BF4
Crabtree, Robert H.,Hlatky, Gregory G.,Parnell, Charles P.,Segmüller, Brigitte E.,Uriarte, Richard J.
, p. 354 - 358 (2008/10/08)
[WH6(PMe2Ph)3], [ReH5(PMe2Ph)3], [ReH7(PPh3)2], [OsH4(PMe2Ph)3], and [IrH5(PPh3)2] react with HBF4 in MeCN (=S) to give [WH2S3(PMe2Ph)3]2+, [ReHS3(PMe2Ph)3]2+, [ReHS4(PPh3)2]2+, [OsS3(PMe2Ph)3]2+, and [IrH2S2(PPh3)2]+ as the BF4 salts. The reaction mechanism and evidence for the initial protonation of some of the d0 polyhydrides at an M-H bond is discussed. In all but the iridium case, MeOH and Me2CO failed to give analogous complexes and no alkane or alkene dehydrogenation reactions were ever observed with the acetonitrile complexes. In the iridium case a variety of solvento complexes can be obtained. Where S = Me2CO, these are active in alkene and alkane dehydrogenation, and in this case a single-crystal X-ray diffraction study was performed: monoclinic unit cell; a = 10.565 (2) ?; b = 25.315 (7) ?; c = 15.460 (4) ?; β = 95.74 (2)°; V = 4114 (4) ?3; space group P21/c; Z = 4; R = 5.6%. The trans influence of the hydride ligands on the O-bound acetone groups was pronounced: Ir-O = 2.228 (5) ? (av), ca. 10% longer than the expected 2.02 ?. This is consistent with the high reactivity of the acetone complex.
