RESUMO
PtCl(2) reacts with C(6)F(5)CN to give trans-[PtCl(2)(NCC(6)F(5))(2)] (1) which, in turn, reacts with carbonyl-stabilized phosphorus ylides Ph(3)P=CHR [R = C(O)Me, CO(2)Et] to give trans-[PtCl(2){NH=C(C(6)F(5))C(=PPh(3))CO(2)Et}{NCC(6)F(5)}] (2a), trans-[PtCl(2){NH=C(C(6)F(5))C(=PPh(3))CO(2)Et}(2)] (3a), trans-[PtCl(2){E-NH=C(C(6)F(5))C(=PPh(3))C(O)Me}(2)] (3b) or trans-[PtCl(2){E-N(=PPh(3))C(C(6)F(5))=CHCO(2)Et}{E-NH=C(C(6)F(5))C(=PPh(3))CO(2)Et}] (4), depending on the reaction conditions. Similarly, Ph(3)P=CHCO(2)Me reacts with trans-[PtCl(2)(NCMe)(2)] to give trans-[PtCl(2){NH=CMeC(=PPh(3))CO(2)Me}(NCMe)] (2b). Complex 3b.CH(2)Cl(2) crystallizes in the triclinic system, space group P&onemacr;, with a = 7.596(2) Å, b = 12.694(3) Å, c = 16.962(3) Å, alpha = 104.28(3) degrees, beta = 102.73(3) degrees, gamma = 104.43(3) degrees, V = 1464.2(6) Å(3), and Z = 1. The structure was refined to values of R1 = 0.0411 and wR2 = 0.1172 [I >2sigma(I)] and shows two chloro and two N-bonded beta-imino phosphorus ylide ligands in a trans geometry. Complex 4 crystallizes in the monoclinic system, space group P2(1)/c, with a = 16.400(8) Å, b = 14.354(7) Å, c = 23.221(12) Å, alpha = 90(3) degrees, beta = 92.42(2) degrees, gamma = 90 degrees, V = 5462(5) Å(3), and Z = 4. The structure was refined to values of R1 = 0.0246 and wR2 = 0.0557 [I >2sigma(I)]. This complex has also a trans-geometry and shows that while the attack of the ylide on one of the nitrile ligands produces a beta-imino-phosphorus ylide ligand the addition on the second nitrile leads to an iminophosphorane ligand.
RESUMO
Transmetalation reactions of the polyimido Sb(III) anions [Sb(3)(NCy)(4)(HNCy)(2)](-), [Sb(2)(NCy)(4)](2)(-), and [Sb(NCy)(3)](3)(-) with metal sources allows the logical assembly of cage compounds containing various mixed-metal stoichiometries. The breadth of this approach is illustrated by the syntheses of [Sb(NCy)(4)(HNCy)(2)]K.2(toluene) (1), containing an early main group metal, [Sb(2)(NCy)(4)](2)M(4) (M = Cu (2), Ag (3)), containing transition metals, and [Sb(NCy)(3)Pb(3)] (4), containing a p-block metal. The low-temperature X-ray structures of complexes 1-4 have been determined. Crystal data: 1, monoclinic, space group C2/c, a = 18.418(3) Å, b = 11.457(2) Å, c = 24.798(6) Å, beta = 90.24(2) degrees, Z = 4; 3, triclinic, space group P&onemacr;, a = 11.501(2) Å, b = 13.752(3) Å, c = 22.868(5) Å, alpha = 103.50(3) degrees, beta = 95.89(3) degrees, gamma = 96.71(3) degrees, Z = 2; 4, triclinic, space group P&onemacr;, a = 11.071(2) Å, b = 14.892(2) Å, c = 17.262(2) Å, alpha = 65.36(3) degrees, beta = 74.21(3) degrees, gamma = 70.70(3) degrees, Z = 2. The structure of 2 has been reported in preliminary form. The K(+) ion of 1 is coordinated by four of the N centers of the [Sb(3)(NCy)(4)(HNCy)(2)](-) ligand. In addition, beta-C(-H).K interactions involving four of the Cy groups and MeC(-H).K interactions involving two toluene molecules give the K(+) ion a 10-coordinate geometry. In 2 and 3, the N centers of two [Sb(2)(NCy)(4)](2)(-) dianions symmetrically coordinate a central M(4) square-planar core. The symmetrical complexation of three Pb(II) centers by two [Sb(NCy)(3)](3)(-) trianions produces an 11-membered polyhedral cage structure in 4.
RESUMO
The reactions of [Sb(NMe(2))(3)] with the primary (amido)lithiums [PhCH(2)CH(2)N(H)Li](n)(), [CyN(H)Li](n)() (Cy = C(6)H(11)), [2,4-dmpN(H)Li](n)() [2,4-dmp = 2,4-(MeO)(2)C(6)H(3)], and [(t)()BuN(H)HLi](n)() give the heterobimetallic cage complexes [{Sb(NCH(2)CH(2)Ph)(3)}(2)Li(6).2THF] (1), [{Sb(NCy)(3)}(2)Li(6).2HNMe(2)].2C(6)H(5)CH(3) (2), [Sb{N(2,4-dmp)}(3)](2)Li(6).2THF.2C(6)H(5)CH(3) (3), and [{Sb(NBu(t)())(3)}(2)Li(6)] (4), respectively. The low-temperature X-ray structures of 1-4 show that they are composed of 14-membered polyhedral cages constructed from the association of two [Sb(NR)(3)](3)(-) trianions with six Li(+) cations. Crystal data; 2, triclinic, P&onemacr;, a = 12.775(6) Å, b = 13.191(9) Å, c = 11.015(5) Å, alpha = 111.55(4) degrees, beta = 95.39(4) degrees, gamma = 115.26(4) degrees; 3, triclinic P&onemacr;, a = 10.435(4) Å, b = 12.654(5) Å, c = 14.278(6) Å, alpha = 75.31(4) degrees, beta = 79.33(4) degrees, gamma = 84.33(4) degrees; 4, monoclinic P2(1)/c, a = 9.994(1) Å, b = 17.421(2) Å, c = 10.680(2) Å, beta = 111.33(1) degrees (the structure of 1 being reported previously). Lewis base solvation of the N(6)Li(6) substructures of 1-3 results in distortion and deformation of the Li frameworks. The structural variations in the cores of 1-4 indicate that the bonding in these species is dominated by the valence and bonding demands of the p block metal centers.