Abstract
Complexes of Osmium(II) and Osmium(III) with the polytertiary phosphines, C
6H
5P[CH
2CH
2P(C
6H
5)
2]
2; (triphos), (C
6H
5)
2PCH
2CH
2P(C
6H
5)CH
2CH
2P(C
6H
5)CH
2CH
2P(C
6H
5)
2 (tetraphos-1), P[CH
2CH
2P(C
6H
5)
2]
3; (tetraphos-2) and C
6H
5{CH
2P[CH
2CH
2P(C
6H
5)
2]
2}
2; (TDDX) are described. Osmium trichloride reacts with triphos, tetraphos-1, and tetraphos-2 in benzene methanol mixture at reflux temperature to give the complexes OsCl
3 (triphos), [OsCl
3(S)]
2 (tetraphos-1) and OsCl
3(tetraphos-2) respectively. The hexatertiary phosphine TDDX, formed only polynuclear complexes with osmium and attempts to prepare mononuclear complexes failed. The ligand TDDX reacted with either osmium trichloride or ammonium hexachloro osmate(IV) in boiling ethanol to give the diamagnetic trinuclear complex Os
3Cl
6(TDDX) and paramagnetic complexes of the type Os
2X
6(TDDX) where XCl or Br). The proton NMR spectra of the complexes are discussed and used along with the IR data to assign configurations.