Kinetic and mechanistic study of the Pt(II) versus Pt(IV) effect in the platinum-mediated nitrile-hydroxylamine coupling.

The metal-mediated coupling between coordinated EtCN in the platinum(II) and platinum(IV) complexes cis- and trans-[PtCl(2)(EtCN)(2)], trans-[PtCl(4)(EtCN)(2)], a mixture of cis/trans-[PtCl(4)(EtCN)(2)] or [Ph(3)PCH(2)Ph][PtCl(n)(EtCN)] (n = 3, 5), and dialkyl- and dibenzylhydroxylamines R(2)NOH (R = Me, Et, CH(2)Ph, CH(2)C(6)H(4)Cl-p) proceeds smoothly in CH(2)Cl(2) at 20-25 degrees C and the subsequent workup allowed the isolation of new imino species [PtCl(n){NH=C(Et)ONR(2)}(2)] (n = 2, R = Me, cis-1 and trans-1; Et, cis-2 and trans-2; CH(2)Ph, cis-3 and trans-3; CH(2)C(6)H(4)Cl-p, cis-4 and trans-4; n = 4, R = Me, trans-9; Et, trans-10; CH(2)Ph, trans-11; CH(2)C(6)H(4)Cl-p, trans-12) or [Ph(3)PCH(2)Ph][PtCl(n){NH=C(Et)ONR(2)}] (n = 3, R = Me, 5; Et, 6; CH(2)Ph, 7; CH(2)C(6)H(4)Cl-p, 8; n = 5, R = Me, 13; Et, 14; CH(2)Ph, 15; CH(2)C(6)H(4)Cl-p, 16) in excellent to good (95-80%) isolated yields. The reduction of the Pt(IV) complexes 9-16 with the ylide Ph(3)P=CHCO(2)Me allows the synthesis of Pt(II) species 1-8. The compounds 1-16 were characterized by elemental analyses (C, H, N), FAB-MS, IR, (1)H, (13)C{(1)H}, and (31)P{(1)H} NMR (the latter for the anionic type complexes 5-8 and 13-16) and by X-ray crystallography for the Pt(II) (cis-1, cis-2, and trans-4) and Pt(IV) (15) species. Kinetic studies of addition of R(2)NOH (R = CH(2)C(6)H(4)Cl-p) to complexes [Ph(3)PCH(2)Ph][Pt(II)Cl(3)(EtCN)] and [Ph(3)PCH(2)Ph][Pt(IV)Cl(5)(EtCN)] by the (1)H NMR technique revealed that both reactions are first order in (p-ClC(6)H(4)CH(2))(2)NOH and Pt(II) or Pt(IV) complex, the second-order rate constant k(2) being three orders of magnitude larger for the Pt(IV) complex. The reactions are intermolecular in nature as proved by the independence of k(2) on the concentrations of added EtC triple bond N and Cl(-). These data and the calculated values of Delta H++ and Delta S++ are consistent with the mechanism involving the rate-limiting nucleophilic attack of the oxygen of (p-ClC(6)H(4)CH(2))(2)NOH at the sp-carbon of the C triple bond N bond followed by a fast proton migration.