Gold derivatives of scorpionates: comparison with the other coinage metal poly(pyrazolyl)borate analogues

Gold derivatives Au(Tpx)(PR3)](Tpx = Tp, hydrotris(pyrazol-1-yl)borate or Tp*, hydrotris(3,5-dimethylpyrazol-1-yl)borate; R = Ph or tBu) and Au(pzTp)(PR3)x](pzTp = tetrakis(pyrazol-1-yl)borate, x = 1 or 2, R = Ph or tBu) have been synthesised and characterized both in solution (1H- and 31P1H]-NMR) and in the solid state (IR, single crystal X-ray structure analysis, 31P CPMAS). 31P 1H] NMR solution data suggest greater stability of the tetrakis(pyrazolyl)borate relative to those of tris(pyrazolyl)borate. All compounds are fluxional at room temperature. In order to compare Au(Tp*)(PPh3)] with analogous coinage metal adducts we have synthesized and structurally characterized Cu(Tp*)(PPh3)] x PPh3 and Ag(Tp*)(PPh3)] x 2MeCN. In Au(Tp*)(PPh3)] the gold atom adopts a distorted tetrahedral geometry with 2.181(5) and 2.37(2) angstroms (cf. 2.166(6), 2.098(1) in Cu(Tp*)PPh3], 2.156(2), 2.075(7) in Cu(Tp*)(PPh3)] x PPh3; and in Ag(Tp*)PPh3] x MeCN 2.347(12), 2.35(5) angstroms). There are three independent Au(Tp*)(PPh3)] molecules in the asymmetric unit of the structure with their PAu...B axes lying on the cell diagonal of a cubic P213 cell, two with the same chirality aligned opposed in direction to the third which is of opposite chirality. A number of Cu, Ag and Au complexes containing scorpionate ligands have also been investigated by 31P cross-polarization magic-angle-spinning (CPMAS) NMR spectroscopy.