Search

The title compound has a quasi-trigonal bipyramidal (or alternatively, distorted octahedral) structure with a symmetrically bound acetate ligand and cis-dioxo ligands in the trigonal plane, and is an effective oxidant for halides, alcohols, sulphides, and phosphines, functioning catalytically in the presence of N-methylmorpholine-N-oxide (NMO) as co-oxidant.

The new salts trans -(R-pyH) 2 [RuO 2 Cl 4 ] (R-py = pyridine and substituted pyridines), trans -R 2 [RuO 2 X 4 ] [X = Cl, Br; R = Me 2 NH(CH 2 ) 2 NHMe 2 , Me 2 N(C 2 H 4 ) 2 NMe 2 ]; (Ph 4 P)[RuO 2 Br 3 ], trans -(Ph 4 P) 2 [RuO 2 Br 4 ] and trans -(Ph 4 As)[RuO 2 Cl 3 (OPPh 3 )] are reported. They function in dichloromethane or acetonitrile as two-electron catalysts for the oxidation of primary alcohols to aldehydes and of secondary alcohols to ketones, without competing olefinic bond cleavage, in the presence of N-methylmorpholine-N-oxide as co-oxidant. Vibrational spectra of the complexes are reported.

The new salts trans -(R-pyH) 2 [RuO 2 Cl 4 ] (R-py = pyridine and substituted pyridines), trans -R 2 [RuO 2 X 4 ] [X = Cl, Br; R = Me 2 NH(CH 2 ) 2 NHMe 2 , Me 2 N(C 2 H 4 ) 2 NMe 2 ]; (Ph 4 P)[RuO 2 Br 3 ], trans -(Ph 4 P) 2 [RuO 2 Br 4 ] and trans -(Ph 4 As)[RuO 2 Cl 3 (OPPh 3 )] are reported. They function in dichloromethane or acetonitrile as two-electron catalysts for the oxidation of primary alcohols to aldehydes and of secondary alcohols to ketones, without competing olefinic bond cleavage, in the presence of N-methylmorpholine-N-oxide as co-oxidant. Vibrational spectra of the complexes are reported.

The new complexes [OsO2(OCOR)Cl2]–[R = Me, Et or CH(Me)Et] and [RuO2(OCOR)Cl2]–(R = Me, Et, Pr or CHF2) have been prepared. In addition to functioning as catalytic oxidants for organic substrates in the presence of N-methylmorpholine N-oxide as co-oxidant, the acetato complexes [MO2(OCOMe)Cl2]– in particular can be used as precursors for a wide variety of complexes. New species prepared from these include [OsO2(NCO)4]2–, [OsO2(SCN)4]2–, [OsO2(acac)Cl2]–(acac = pentane-2,4-dionate), [Os(terpy)Cl3]+(terpy = 2,2′ : 6′,2″-terpyridine), [OsO2(S2CNEt2)2] and [Ru(OH)(H2O)(O2COCR1R2)Cl2](R1= R2= Me or Et; R1= Me, R2= Et or Ph).

The title compound has a quasi-trigonal bipyramidal (or alternatively, distorted octahedral) structure with a symmetrically bound acetate ligand and cis-dioxo ligands in the trigonal plane, and is an effective oxidant for halides, alcohols, sulphides, and phosphines, functioning catalytically in the presence of N-methylmorpholine-N-oxide (NMO) as co-oxidant.

Reaction of [PPh4][MCl3(PMe2Ph)](M = Pt or Pd) with [Sn(S2N2)Me2]2 leads to [M(S2N2H)Cl-(PMe2Ph)]; similarly K[PtCl3(C2H4)] reacts to give [Pt(S2N2H)Cl(C2H4)]. The complex [Pt(S2N2H)Cl(PMe2Ph)](1a) is also formed in the reaction of S4N4 with [PtCl2(PMe2Ph)2] at 160 °C, together with [Pt(S3N)Cl(PMe2Ph)](2); S415N4 reacts to give 15N-enriched (1a) and (2), the 31P n.m.r. spectra of which show the presence of both 2J- and 4J-(15N–31P) couplings.