Preparation and X-ray structures of Cu(I), Ni(II), and Pd(II) (N,S) complexes of the monoanion [(tBuN)(S)P(mu-N(t)Bu)2P(S)(NH(t)Bu)]- and a Pt(II) (S,S') complex of the dianion [((t)BuN)(S)P(mu-N(t)Bu)2P(S)(N(t)Bu)]2-.
The metathetical reactions of the lithium derivative of the monoanion [((t)BuN)(S)P(mu-N(t)Bu)(2)P(S)(NH(t)Bu)](-) (L) with CuCl/PPh(3), NiCl(2)(PEt(3))(2), PdCl(2)L'(2) (L' = PhCN, PPh(3)), and PtCl(2)(PEt(3))(2) produced the complexes (PPh(3))CuL (5), NiL(2) (6), PdCl(L)(PPh(3)) (7), PdL(2) (8), and Pt(PEt(3))(2)[((t)BuN)(S)P(mu-N(t)Bu)(2)P(S)(N(t)Bu)] (9). The X-ray structures of 5, 6, and 8 reveal a N,S-coordination for the chelating monoanion L with the metal centers in trigonal planar, tetrahedral, and square planar environments, respectively. By contrast, the dianionic ligand in the square planar Pt(II) complex 9 is S,S'-chelated to the metal center. (31)P NMR spectra readily distinguish between the N,S and S,S' bonding modes, and, on that basis, N,S chelation is inferred for the Pd(II) complex 7. Crystal data: 5, monoclinic, P2(1)/c, a = 19.175(4) A, b = 20.331(4) A, c = 10.017(6) A, beta = 91.79(3) degrees, V = 3903(2) A(3), and Z = 4; 6, orthorhombic, Pbcn, a = 14.298(5) A, b = 15.333(5) A, c = 24.378(5) A, beta = 90.000(5) degrees, V = 5344(3) A(3), and Z = 4; 8, monoclinic, P2(1)/n, a = 13.975(3) A, b = 14.283(3) A, c = 15.255(4) A, beta = 116.565(18) degrees, V = 2723.5(11) A(3), and Z = 2; 9, monoclinic, P2(1)/n, a = 12.479(6) A, b = 21.782(7) A, c = 17.048(5) A, beta = 100.30(3) degrees, V = 4559(3) A(3), and Z = 4.
Chivers
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Department of Chemistry, University of Calgary, Calgary, Alberta, Canada T2N 1N4. chivers@ucalgary.ca
Fedorchuk
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Krahn
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Parvez
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Schatte
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