Unusual Reactivity Mode of Coordinated Oximes: Platinum(IV)-Assisted Ring Closure by Reaction with Acetone.
The platinum(II) complexes trans-[PtCl(2)(RR'C=NOH)(2)], where R = R' = Me, RR' = (CH(2))(4) and (CH(2))(5), react with m-chloroperoxybenzoic acid in Me(2)CO to give the platinum(IV) complexes [PtCl(2)(OCMe(2)ON=CRR')(2)] in 50-60% yields. The complexes [PtCl(2)(OCMe(2)ON=CRR')(2)] were characterized by elemental analysis, EI-MS, and IR and Raman spectroscopies; X-ray structure analyses were performed for both trans-[PtCl(2)(OCMe(2)ON=CC(4)H(8))(2)] and trans-[PtCl(2)(OCMe(2)ON=CC(5)H(10))(2)]. The former compound crystallizes in the triclinic space group P&onemacr; with a = 8.088(2) Å, b = 8.327(2) Å, c = 8.475(2) Å, alpha = 103.54(3) degrees, beta = 102.15(3) degrees, gamma = 108.37(3) degrees, V = 501.0(2) Å(3), Z = 1, and rho(calcd) = 1.917 g cm(-)(3). The latter complex crystallizes in the monoclinic space group C2/c with a = 12.5260(10) Å, b = 9.3360(10) Å, c = 18.699(2) Å, beta = 98.320(10) degrees, V = 2163.7(4) Å(3), Z = 4, and rho(calcd) = 1.862 g cm(-)(3). The structures of [PtCl(2)(OCMe(2)ON=CC(4)H(8))(2)] and [PtCl(2)(OCMe(2)ON=CC(5)H(10))(2)] show an octahedron of Pt where two Cl atoms and two chelate ligands are mutually trans, respectively.
Kukushkin
Vadim Yu.
VY
Department of Chemistry, St. Petersburg State University, 198904 Stary Petergof, Russian Federation, L. Ya. Karpov Physico-Chemical Institute, Obukha Str. 10, 103064 Moscow, Russian Federation, and Departamento de Química Inorgánica, Universidad Autónoma de Madrid, 28049 Madrid, Spain.
Belsky
Vitaly K.
VK
Tudela
David
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