The platinum(II) compounds trans-[PtX(2)(RR'C=NOH)(2)] [X = Cl, R = R' = Me, RR' = (CH(2))(4), (CH(2))(5); X = Br, R = R' = Me] react with m-chloroperoxybenzoic acid (MCPBA) in dimethylformamide to give the platinum(II) complexes [PtX(2){N(=O)CRR'ONCRR'}] containing coordinated nitrosoalkane ligands. The complexes [PtX(2){N(=O)CRR'ONCRR'}] were characterized by elemental analysis, EI-MS, IR, electronic absorption, and (1)H NMR spectroscopy; X-ray structure analysis was performed for [PtCl(2){N(=O)CC(5)H(10)ONCC(5)H(10)}]. The latter compound crystallizes in the triclinic P&onemacr; space group with a = 9.214(2) Å, b = 9.577(2) Å, c = 10.367(2) Å, alpha = 109.14(2) degrees, beta = 91.87(2) degrees, gamma = 115.62(2) degrees, V = 762.8(3) Å(3), Z = 2, and rho(calcd) = 2.135 g cm(-)(3). The reaction between trans-[PtX(2)(RR'C=NOH)(2)] and MCPBA displays a solvent dependence: interaction of these reagents in ketones, R(1)R(2)C=O, yields the platinum(IV) chelates [PtX(2)(OCR(1)R(2)ON=CRR')(2)], while the oxidation state of the oxime N atom remains unchanged. Heating [PtCl(2)(OCR(1)R(2)ON=CRR')(2)] in DMF or in DMF-d(7) at 100 degrees C leads to the extrusion of R(1)R(2)C=O and the formation of [PtCl(2){N(=O)CRR'ONCRR'}].

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In the title compound, trans-[PtCl2(C7H9N)2], the PtII atom is located on an inversion center and is coordinated by two 3,4-dimethyl­pyridine ligands and two chloride ligands, resulting in a typical slightly distorted square-planar geometry. The crystallographic inversion centre forces the value of the C—N—N—C torsion angle to be linear and the 3,4-dimethyl-pyridine ligands to be coplanar.

Addition compounds of MoO 2 Br 2 are useful precursors for the synthesis of species that are relevant in catalytic chemical and biochemical oxotransfer processes. 1 Also, molybdenum bromides are on the borderline of stability for þ 5 and þ 6 oxidation states of the metal, which makes them potentially useful for redox studies. These compounds are usually prepared by treating MoO 2 Br 2 with the appropriate ligand in aprotic solvents, 2 and in a few cases by addition of the ligand to a solution of H 2 MoO 4 Á H 2 O in HBr. 3 However, the presence of MoO 2 Br 2 (H 2 O) 2 in solutions of alkali molybdates in concentrated hydrobromic acid 4 and the extractability of this species with diethyl ether suggest that a number of addition compounds could be readily accessible from commercial sodium molybdate. In this manner a number of adducts with O-donor ligands can be isolated. 5 Here we describe the preparation of the outer-sphere, hydrogen-bonded complex MoO 2 Br 2 (H 2 O) 2 Á diglyme as well as those of the adducts MoO 2 Br 2 (L) 2 ,