SYNTHESIS OF 3-COORDINATE AND 4-COORDINATE COINAGE METAL [ML3][X], [MXL3], AND [ML4][X] COMPLEXES - CRYSTAL-STRUCTURES OF [CU(P(P-C6H4OME)3)3][CLO4] AND [CU(SB(P-C6H4F)3)4][BF4]

Forty-nine complexes of the type [M{Z(Ph)m(p-C6H4Y)3-m}n][X] M = Cu, Ag; X = BF4, ClO4; Z = P, As Sb; Y = Cl, F, Me, OMe; n = 3, 4; m = 0-2) have been prepared and characterized with the intent of demonstrating electronic control of their sterechemistry. With electron-withdrawing substituents (Y = Cl, F), primarily n = 3 complexes are formed. IR spectra are, however, characteristic of coordinated anions, indicating the existence of 4-coordinate complexes. In a few instances, where M = Cu, Z = Sb, and Y = F, n = 4 complexes are isolated. For electron-donating substituents (Y = Me, OMe), both n = 3 and n = 4 complexes are obtained, with n = 3 preferred for Cu and n = 4 dominating for Ag. Coordination of the anions is generally not anticipated for the n = 3 complexes, based on the IR spectra. One Ag complex with n = 2 was isolated. Crystals of [Cu{P(p-C6H4OMe)3}][ClO4] are in the rhombohedral space group R3bar, with a = 19.423 (7) angstrom, c = 27.616 (18) angstrom, and Z = 6 at T = 120-degrees-C. The structural refinement converged to R = 0.098. The structure consists of isolated [CuL3]+ cations cations and [ClO4]anions. The Cu atom is 3-coordinate, with the Cu atom lying only 0.23 angstrom out of the plane of the three phosphorus atoms. The [Cu{Sb(p-C6H4F)3}4][BF4] salt is trigonal, space group P31c, with a = 13.489 (1) angstrom, c = 23.327 (3) angstrom, and Z = 2 at 22-degrees-C. The structure refined to R = 0.052. The 4-coordinate Cu atom is located at a site of C3 symmetry, with three Sb atoms at 2.556 (1) angstrom and one at 2.547 (1) angstrom.