SYNTHESIS AND STRUCTURE OF COPPER(I), SILVER(I) AND ZINC(II) AMIDES [CU2(MPSA)2], [CU6X2(MPSA)4] (X = CL OR BR), [AG4(MPSA)4] AND [(ZNET)2(MPSA)2] [MPSA = 2-N(SIME3)-C5H3N-6-ME]

The copper(I) amide [Cu2(mpsa)2] 1 and its 1:1 adduct with CuX, [Cu6(mpsa)4X2] (X = Cl, 2a or Br, 2b) {mpsa = [2-(6-methyl)pyridyl]trimethylsilylamido, 2-N(SiMe3)C5H3N-6-Me}, the silver(I) amide [Ag4(mpsa)4] 3 and the zinc(II) amides [(ZnEt)2(mpsa)2] 4, [ZnCl(mpsa)] 5, and [Zn(mpsa)2] 6, have been prepared from lithium reagents and the appropriate metal halide, and Hmpsa and ZnEt2 (4 and 6). The amides 1-4 have been characterized crystallographically. In 1 the ligands span the two metal centres with Cu-N(amido) 1.875(4), 1.887(4), angstrom, Cu-N(pyridyl) 1.902(4), 1.903(4) angstrom, N-Cu-N 174.6(2), 173.4(2)-degrees, and Cu...Cu 2.420(1) angstrom. Complexes 2a and 2b are isomorphous diethyl etherates; mpsa ligands span three metal centres with each N(amido) bridging (i) a two-co-ordinate copper, the other co-ordination site being another N(amido), Cu-N 1.893(6)-1.927(7) angstrom, 2a, 1.884(9)-1.919(8) angstrom, 2b, and (ii) a three-co-ordinate copper bound by the amido centre, Cu-N, 2.100(6)-2.133(6) angstrom, 2a, 2.100(8)-2.152(9) angstrom, 2b, a pyridyl N-centre, 1.993(7)-2.006(7) angstrom, 2a, 1.983(9)-2.013(8) angstrom, 2b, and a halide, Cu-X 2.270(3)-2.303(3) angstrom, 2a, 2.409(3)-2.410(2) angstrom, 2b. Complex 3 is a hexane solvate; mpsa ligands link four silver atoms in a plane; two silver atoms lie on a C2 axis and are two-co-ordinate, bound by pairs of N(pyridyl) groups; Ag-N, 2.140(3), 2.169(6) angstrom with N-Ag-N, 169.3(2), 171.2(2)-degrees; the other (symmetry-related) pair are two-co-ordinate, bound by pairs of N(amido) groups: Ag-N, 2.099(3), 2.097(4), with N-Ag-N, 168.6(2)-degrees. In complex 4 the N(amido) groups bridge the metal centres with N(pyridyl) forming chelate rings on the same side of a Zn2N2 plane; Zn-N(pyridyl) 2.125(5), 2.108(5) angstrom, Zn-N(amido) 2.061(5), 2.072(5) angstrom (chelate ring), 2.245(5), 2.225(5) angstrom, Zn...Zn 2.958(2) angstrom. Compound 1 forms an adduct with trimethylphosphine, [Cu(mpsa)(PMe3)2] 7.