112490-02-5

Upstream product

• 133377-32-9 OsHCl(phosphorus trichloride)(CO)(triphenylphosphine)2 
• 22560-16-3 lithium triethylborohydride 

Downstream Products

• 116868-12-3 OsH(η1-OC{O}CF3)(PH3)(CO)(PPh3)2 
• 116913-30-5 {OsH(PH₃)(NCCH₃)(CO)(PPh₃)2}ClO₄ 

Relevant academic research and scientific papers

Reactions of coordinated phosphorus trichloride, phenylphosphonous dichloride, 1-phenyl-3,4-dimethylphosphole and mesitylphosphine in osmium(II) complexes

Substitution of a single labile triphenylphosphine ligand in OsHCl(CO)(PPh3)3 by PCl3, PCl2Ph, PhH or PH2(mesityl) gives complexes with the new ligand trans to the hydride ligand and mutually cis to the two triphenylphosphine ligands.The PCl3 and PCl2Ph complexes undergo slow substitution reactions at phosphorus, at temperatures > 50 deg C, with the nucleophiles methoxide, toluidine and hydride.The hydride ligand is readily cleaved either by acetonitrile solutions of aqueous perchloric acid, to give cationic acetonitrile conta ining complexes or by chlorine, to give neutral dichloride complexes.In all but one instance the products are isolated as mixtures of isomeric complexes with trans triphenylphosphine ligands.An exception to this dominant stereochemistry is observed for the complex containing the bulky mesitylphosphine ligand, OsHCl(PH2mesityl)(CO)(PPh3)2 for which the product of the hydride cleavage and subsequent carbonylation reaction consists of an almost equal mixture of isomers of ClO4 with cis and trans triphenylphosphine ligands.The structure of one of these isomers, with a mesitylphosphine trans to triphenylphosphine, has been determined by X-ray crystallography.

Phosphine (PH3) complexes of ruthenium, osmium and iridium as precursors of terminal phosphido (PH2) complexes and the crystal structure of 2-PH2)Cl(CO)(PPh3)2>2.(C2H2Cl4)4

Stable phosphine complexes MHCl(PH3)(CO)(PPh3)2 (M = Os, 1a, M = Ru, 1b) and IrHXCl(PH3)(PPh3)2 (X = H, 2, X = Cl, 3) have been prepared by substitution of phosphine for a labile triphenylphosphine in tris(triphenylphosphine) precursors.Strong acids (e.g. aqueous HClO4 in CH3CN) cleave the hydride-metal bonds in 1a, 1b to give ClO4 (9a, 9b) as a mixture of isomeric complexes.The ligands Cl-, PMe3, and CO can be substituted for the labile acetonitrile in 9a to give OsCl2(PH3)(CO)2(PPh3)2 (12) ClO4 (10) and ClO4 (11), respectively.Base deprotonates 10 and 11 to give stable isolable terminal phosphido complexes OsCl(PH2)L(CO)(PPh3)2 (L = CO, 14, L = PMe3, 15), but when 9a is deprotonated, acetonitrile is also lost and a dimeric complex 2-PH2)Cl(CO)(PPh3)2>2 (13) is formed.The colourless crystals of 13 are triclinic with space group P1, a 14.101(4), b 15.091(5), c 11.708(5) Angstroem, α 96.68(3), β 91.71(3), γ 63.92(2) deg, Z = 1, V = 2222.0 Angstroem3.The final refinement gave R = 0.0589, Rw = 0.0603 for 4865 observed reflections.Phosphine oxidatively adds to Os(CO)2(PPh2)3 to give the stable hydride-phosphido-complex, OsH(PH2)(CO)2(PPh3)2 (19).