104469-34-3Relevant 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.
THE REACTIONS OF FREE AND SURFACE ANCHORED PHOSPHINES WITH MULTIDENTATE LIGAND STABILISED METAL CARBONYL CLUSTER COMPLEXES
Foster, Douglas F.,Harrison, Jane,Nicholls, Barry S.,Smith, Anthony K.
, p. 99 - 108 (2007/10/02)
The trinuclear, bidentate-phosphine stabilised cluster complexes, M3(CO)10(dppm) undergo selective substitution by monodentate phosphines, L, to give M3(CO)9(dppm)L in which
