18974-23-7

Upstream product

• 22372-70-9 tetracarbonyldihydroosmium 
• 25838-88-4 [OsH(CO)3(P(C₆H₅)3)2]⁽¹⁺⁾*ClO₄^(1-)=[OsH(CO)3(P(C₆H₅)3)2]ClO₄ 
• 260049-76-1 osmium(IV) trihydrido(trimetylsilyl)(CO)(triphenylphosphine)2 complex 
• 201230-82-2 carbon monoxide 

Downstream Products

• 113474-38-7 [Os(CH₃C₆H₄SO₃)2(CO)2(P(C₆H₅)3)2] 
• 105811-91-4 [Os(C₁₀H₁₅O₄S)2(CO)2(P(C₆H₅)3)2] 
• 105811-90-3 dicarbonylbis(toluene-p-sulphonato)bis(triphenylphosphine)osmium(II) 
• 10170-15-7 OsCl₂(P(C₆H₅)3)2(CO)2 
• 105812-06-4 dicarbonylbis(trifluoromethanesulphonato)bis(triphenylphosphine)osmium(II) 

Relevant academic research and scientific papers

The synthesis, structure, and reactivity of the osmium(IV) trihydrido silyl complex, OsH3(SiMe3)(CO)(PPh3)2

Reaction between the five coordinate complex, Os(Ph)Cl(CO)(PPh3)2, and HSiMe3 produces the osmium(IV) trihydrido silyl complex, OsH3(SiMe3)(CO)(PPh3)2 (1). The structure of 1 has been determined by single crystal X-ray crystallography and by multi-nuclear NMR spectroscopy. The structure has an approximately tetrahedral disposition of silyl, carbonyl and the two PPh3 ligands about osmium with the three classical hydride ligands located, one trans to CO, and the other two each approximately trans to a PPh3. Treatment of complex 1 with HSiR3 (R=Et, Ph), HSn(p-tolyl)3, or HC2Ph gives OsH3(SiR3)(CO)(PPh3)2 (R=Et (2), Ph (3)), OsH2[Sn(p-tolyl)3]2(CO)(PPh3)2 (4) or OsH(C2Ph)(CO)(PPh3)3 (5), respectively. A likely intermediate in these reactions is the coordinatively unsaturated complex, OsH2(CO)(PPh3)2.

A Radical-Chain Mechanism for Dinuclear C-H Bond Formation

Both the formation of (Ph3PAu)2Os(CO)4 from Ph3PAuCH3 and H2Os(CO)4 and the formation of (Ph3PAu)Mn(CO)5 from Ph3PAuCH3 and HMn(CO)5 occur by radical-chain mechanisms.The chain carriers are .Mn(CO)5 and .Os(H)(CO)4, respectively, arising from hydrogen atom abstraction from the initial hydrides.Photolysis of a small amount of the appropriate dimer (Mn2(CO)10 or H2Os2(CO)8) generates the chain carrier and thus initiates the reaction.No such reaction occurs between Ph3PAuCH3 and HRe(CO)5, even in the presence of substantial amounts of .Re(CO)5.The formation of H2Os(CO)3PPh3 from Ph3P and H2Os(CO)4 also occurs by a radical-chain mechanism with .Os(H)(CO)4 as the chain carrier, and the reactions of Ph3PAuCH3 and Ph3P with H2Os(CO)4 can be simultaneously initiated.

SYNTHESIS, STRUCTURE AND REACTIONS OF A dihapto-FORMALDEHYDE COMPLEX, Os(η2-CH2O)(CO)2(PPh3)2

Os(η2-CH2O)(CO)2(PPh3)2 results from direct reaction of formaldehyde with the zerovalent complex, Os(CO)2(PPh3)3.The structure of Os(η2-CH2O)(CO)2(PPh3)2 was determined by X-ray crystallography.The crystals are triclinic, space group P, a 18.739(2), b 11.157(1), c 9.986(1) Angstroem, α 116.70(1), β 93.20(1), γ 107.93(1) deg, V 1727.69 Angstroem3, Z = 2, Dm 1.55(2), Dc 1.57 g cm-3.Refinement of atomic parameters was by full-matrix least-squares methods, employing anisotropic thermal parameters for all non-hydrogen atoms except for the carbon atomsof the phenyl rings.The formaldehyde hydrogen atoms were located from difference electron density maps, other hydrogens were included in calculated positions.Final residuals were R = 0.047 and Rw = 0.061 for 3508 unique observed reflections measured on an automatic diffractometer.The complex itself is monomeric, although interstices in the crystal lattice are occupied by hydrogen-bonded water dimers which fulfil a purely space-filling role.The osmium is bonded to two mutually trans triphenylphosphines, two carbonyls, and the η2-formaldehyde, in an arrangement which is best described as distorted octahedral.The geometry of the coordinated formaldehyde is characterised by Os-O 2.039(7), Os-C 2.186(8) and C-O 1.584 (11) Angstroem.The Os-P bonds are equivalent at 2.372(2) and 2.378(2) Angstroem but the Os-CO bond trans to the formaldehyde carbon 1.931(7) Angstroem is longer than that trans to the formaldehyde oxygen 1.907(7) Angstroem.Os(η2-CH2O)(CO)2(PPh3)3 has proved to be a useful synthetic precursor for stable formyl, hydroxymethyl, methoxymethyl, and halomethyl (CH2X, X = Cl, Br, I) complexes.The compoundsOs(CHO)H(CO)2(PPh3)2, Os(CH2OH)H(CO)2(PPh3)2, Os(CH2OMe)Cl(CO)2(PPh3)2 and Os(CH2Cl)Cl(CO)2(PPh3)2 are illustrative of the many compounds which have been characterised.A general synthetic route to neutral formyl osmium complexes, Os(CHO)X(CO)2(PPh3)2 (X = halide or alkyl) has been developed from reaction of the cations + with BH4-.Acetaldehyde also reacts with Os(CO)2(PPh3)3 forming Os(η1-CCH3)H(CO)2(PPh3)2.No reaction was observed with benzaldehyde, and trichloroacetaldehyde affords the cation, +.