150676-41-8Relevant academic research and scientific papers
A comparative study of the reactivity of the lightly stabilized cluster [Os3(CO)8{μ3-Ph2PCH2P(Ph)C 6H4}(μ-H)] towards tri(2-thienyl)-,tri(2-furyl)- and triphenyl-phosphine
Raha, Arun K.,Uddin, Md. Nazim,Ghosh, Shishir,Miah, Abdur R.,Richmond, Michael G.,Tocher, Derek A.,Nordlander, Ebbe,Hogarth, Graeme,Kabir, Shariff E.
, p. 399 - 411 (2014/03/21)
Reactions of the lightly stabilized triosmium cluster [Os 3(CO)8{μ3-Ph2PCH 2P(Ph)C6H4}(μ-H)] with tri(2-thienyl) phosphine (PTh3) and tri(2-furyl)phosphine (PFu3) are described and compared to analogous reactions with PPh3. At room temperature, a number of products are isolated: [Os3(CO) 10(μ-dppm)] from CO addition, [Os3(CO) 8(PR3){μ3-Ph2PCH 2P(Ph)C6H4}(μ-H)] from phosphine addition, [Os3(CO)9(PR3)(mdppm)] from phosphine and CO addition and [Os3(CO)8(PR3)2(μ-dppm)] from addition of two equivalents of phosphine. The latter are shown by NMR and X-ray diffraction to exist as 1,2-isomers, whereby one phosphine is bound to the non-dppm-substituted center and the second shares an osmium atom with one end of the diphosphine. Heating 1,2-[Os3(CO)8(PTh 3)2(μ-dppm)] at 100 °C results in its clean isomerization to the 1,1-isomer in which both monodentate phosphines are located on the same osmium atom. Prolonged heating of [Os3(CO) 8(PR3)2(μ-dppm)] (R = Th, Ph) at 110 °C gives [Os3(CO)9(PR3)(mdppm)] and the new lightly stabilized clusters [Os3(CO)7(PR 3){μ3-Ph2PCH2P(Ph)C 6H4}(μ-H)], the latter being formed by loss of phosphine and CO with concurrent metalation of a phenyl ring. Heating [Os 3(CO)8(PFu3)2(μ-dppm)] at 110 °C gives [Os3(CO)9(PFu3)(μ-dppm)] together with the carbonphosphorus bond cleavage products [Os 3(CO)7(μ-PFu2)(μ3- η2-C4H2O)(μ-H)(μ-dppm)] and [Os 3(CO)7(μ-PFu2)(μ3- η2-C6H3CH3)(μ-H)(μ-dppm)]. All new compounds were characterized by analytical and spectroscopic techniques together with single crystal X-ray diffraction analysis of nine clusters. Density functional theory (DFT) calculations have been carried out on isomers of [Os3(CO)8(PR3)2(μ-dppm)] in order to understand the observed isomer ratios.
Reaction of the Unsaturated Triosmium Clusters > and > with Phosphines and Phosphites; Crystal Structures of (PPri3>, 2>, and <
Brown, Michael P.,Dolby, P. Ann,Harding, Marjorie M.,Mathews, A. Jane,Smith, Anthony K.
, p. 1671 - 1680 (2007/10/02)
Treatment of the unsaturated clusters > 1a and >1b with two-electron donor ligands gave the saturated clusters L> L = CO 2a or PR3 or P(OR)3 3 (
