Synthesis and structures of copper and gold complexes of the P,N ligands RNdouble bond; length as m-dashC(But)C(H)RPPh2 (R = SiMe3, H)

The reaction of the chelating P,N ligand RNdouble bond; length as m-dashC(But )CH(R)PPh2 (R = SiMe3) (1) with CuCl and CuCl2 (probably by way of reduction to Cu(I) by the phosphine ligand) or Cu(NCCH3)4ClO4 yielded the dimeric 1:1 complex [Cu{PPh2CH(R)C(But )double bond; length as m-dashNR}Cl]2 (2) or the monomeric 2:1 complex [Cu{PPh2CH(R)C(But )double bond; length as m-dashNR}2]ClO4 (3), respectively. The presence of trace amounts of water during the reaction resulted in the successive cleavage of the two trimethylsilyl groups of the ligand and the formation of the monomeric chelate complexes [Cu{PPh2CH(R)C(But )double bond; length as m-dashNH}2]ClO4 (4) and [Cu{PPh2CH2C(But )double bond; length as m-dashNH}2]ClO4 (5). Oxidation of 5 by atmospheric oxygen led to small quantities of the blue Cu(II) complex [Cu{(O)PPh2CH2C(But )double bond; length as m-dashNH}2](ClO4)2 (6). The dimeric gold complexes [Au{PPh2CH2C(But )double bond; length as m-dashNH}]2X2 (X = BF4, ClO4) (7) were similarly obtained from the previously described Au{PPh2CH(R)C(But )double bond; length as m-dashNR}Cl by replacing the covalently bound chlorine with the weakly coordinating anions View the MathML sourceClO4-andBF4- in the presence of small quantities of water. The solution and solid state structures (except 5) of all complexes were determined by NMR spectroscopy and X-ray crystallography.