79230-52-7Relevant academic research and scientific papers
SYSTEMATIC SYNTHESIS AND CHARACTERISATION OF PHOSPHIDO-BRIDGED TRIOSMIUM CARBONYL CLUSTERS
Colbran, Stephen B.,Johnson, Brian F. G.,Lewis, Jack,Sorrell, Robert M.
, p. C1 - C5 (2007/10/02)
Phosphine-substituted triosmium clusters Os3(CO)11PR1R2H (a: R1=R2=H; b: R1=Ph, R2=H; c: R1,R2=Ph) have been found to yield, via a deprotonation/protonation sequence, the phosphido-bridged clusters (μ-H)Os3(CO)10-(μ-PR1R2): the intermediate anions 1R2))-> and 1))-> in this systematic synthesis are described.
THE REACTION OF Ru3(CO)12 AND Os3(CO)12 WITH PH2Ph; THE X-RAY CRYSTAL STRUCTURES OF HRu3(CO)10(PHPh) AND H2Ru3(CO)9(PPh)
Iwasaki, Fujiko,Mays, Martin J.,Raithby, Paul R.,Taylor, Philip L.,Wheatley, Peter J.
, p. 185 - 206 (2007/10/02)
Twelve new trinuclear complexes containing terminal PH2Ph, edge-bridging PHPh and/or capping PPh ligands have been isolated from the reaction of M3(CO)12 (M=Ru or Os) with PH2Ph in refluxing solvents.HRu3(CO)10(PHPh) (IIIa) crystallises in the monoclinic space group P21/c with a=8.761(3), b=11.402(4), c=22.041(7) Angstroem, β=98.89(2)deg, and Z=4.The structure was solved by a combination of direct methods and Fourier difference techniques, and refined by blocked-cascade least squares to R=0.027 for 3676 unique observed intensities.The X-ray analysis shows that one edge of the Ru3 triangle is bridged by a hydride and the PHPh ligand, and that the phosphorus-bound hydrogen atom lies over the metal triangle and the phenyl group away from it.This provides an explanation for the ready formation of the capped species H2Ru3(CO)9(PPh) (Va) on pyrolysis of the edge-bridged complex as opposed to the previously reported conversion of HOs3(CO)10(NHPh) to an orthometallated derivative under similar conditions.An X-ray analysis of H2Ru3(CO)9(PPh) (Va) confirms the capped geometry.The complex crystallises in the monoclinic space group P21/n with a=9.323(4), b=15.110(6), c=45.267(15) Angstroem, β=91.84(3) deg, and Z=12.The structure was solved and refined using the same techniques as described previously.The final residual R is 0.061 for 4839 reflections.Some reactions of Va show that the phosphorus cap is difficult to displace and stabilises the molecule with respect to decomposition to non-cluster species.
SYNTHESES AND CHARACTERISATION OF , 2-H)Os3(CO)10(μ2-PRH)> (R=C6H5, p-CH3OC6H4, C6H11) AND 2-H)2Os3(CO)9(μ2-PR)> (R=C6H5, C6H11). INTERCONVERSION OF CLUSTER-BOUND PHOSPHINE AND PHOSPHIDO LIGANDS. CRYSTAL AND MOLECULAR STRUCTURES OF2-H).....
Natarajan, Karuppannan,Zsolnai, Laszlo,Huttner, Gottfried
, p. 365 - 382 (2007/10/02)
Monoorganophosphines react with Os3(CO)12 in presence of trimethylamine oxide to give the phosphine-substituted cluster and the phosphido-bridged hydrido cluster (R=C6H5, p-CH3OC6H4, C6H11).The thermolysis of gave, under different conditions, and , and the thermolysis of gave (R=C6H5, C6H11).All the compounds have been studied by IR, NMR (31P and 1H) and mass spectrometry.The structures of and have been determined by X-ray crystallography.The results obtained for the system Os3(CO)12/PRH2 demonstrate a stepwise transformation of a terminally bonded PRH2 ligand to a doubly bridging μ2-PRH unit and finally to a triply bridging μ3-PR group by successive hydrogen transfer and CO substitution processes.
