518003-88-8Relevant articles and documents
Osmacycles containing the {(Ph2PE)2N}- ligand (E = S or Se): Synthesis and crystal structures
Parr, Jonathan,Smith, Martin B.,Elsegood, Mark R.J.
, p. 85 - 93 (2007/10/03)
The reaction of (Ph2P)2NH (dppa) or Ph2PN(H)P(O)Ph2 (HL) with [Os(η6-cym)Cl2]2 [cym = p-CH3C6H4CH(CH3)2] in THF affords the orange, neutral mononuclear complexes [OsCl2(η6-cym)P-dppa] (1a) or [OsCl2(η6-cym)P-HL] (2), respectively, bearing a pendant -PPh2 or -P(O)Ph2 group. Complex 1a isomerises smoothly in CDCl3 solution to give the cationic P,P′-chelate complex [OsCl(η6-cym)P,P′-dppa]Cl (1b). Compound 2 can further be converted into the yellow P,O-chelate complexes [OsCl(η6-cym)P,O-HL][BF4] (3) and [OsCl(η6-cym)P,O-L] (4) [L = Ph2PNP(O)Ph2] upon treatment with either Ag[BF4] or 1BuOK, respectively. Chloro bridge cleavage of [Os(η6-cym)Cl2]2 with the potassium salt of either {Ph2P(S)}2N- or {Ph2P(Se)}2N- yields the orange neutral complexes [OsCl(η6-cym){E,E′-Ph2P(E)}2N] (E = S 5, E = Se 6). All new compounds were characterised by a combination of NMR spectroscopy (1H and 31P{1H}), IR spectroscopy, microanalysis and X-ray crystallography. The five- (Os-P-N-P-O) and six-membered (Os-E-P-N-P-E) osmacycles represent the first examples of crystallographically characterised osmium(II) metallocycles.
