83096-30-4Relevant academic research and scientific papers
Oxidation and acidolysis of MoH4(PR3)4
Rhodes, Larry F.,Zubkowski, Jeffrey D.,Folting, Kirsten,Huffman, John C.,Caulton, Kenneth G.
, p. 4185 - 4192 (1982)
MoH4(PMe2Ph)4 reacts with 2 mol of AgBF4 in MeCN to give [MoH2(PMe2Ph)4(NCMe)2](BF 4)2, characterized by spectroscopic methods and X-ray crystallography as containing a fluxional dodecahedral dication. Reaction with equimolar AgBF4 gives no new product but only a reduced yield of the same salt. This oxidation is thus followed by reductive elimination of H2 so that the molybdenum oxidation state suffers no net change. The same salt is obtained by treating the tetrahydride with 2 mol of HBF4·OEt2 in acetonitrile. The identity of the phosphine affects the product isolated: MoH2(PMePh2)4, upon treatment with AgBF4 or HBF4·OEt2 in MeCN, yields MoH2(PMePh2)3(NCMe)32+ with liberation of 1 mol of PMePh2. Possible mechanisms are discussed, as is the relationship between silver oxidation and acidolysis. Crystallographic data (at -160°C) for [MoH2(PMe2Ph)4(NCMe)2](BF 4)2: monoclinic space group P21 with a = 12.359 (6) A?, b = 33.323 (2) A?, c = 13.048 (6) A?, β = 128.61 (2)°, Z = 4. R(F) = 0.0673 for 5037 data collected by diffractometer.
