Copper(I) and gold(I) complexes with cis-bis(diphenylphosphino)ethylene. Crystal structures and 31P cross-polarization magic angle spinning nuclear magnetic resonance studies

• DOI: 10.1039/dt9920003357
• Publication Date: 2004-04-07T09:43:05Z
• Authors: Susan J. Berners-...; Lynda A. Colquhoun; Peter C. Healy; Karl A. Byriel; John V. Hanna
• Keywords: Magic angle spinning; Monoclinic crystal system; Orthorhombic crystal system

The synthesis, structural and solid-state 31P cross-polarization magic angle spinning (CP MAS) NMR characterization of cis-bis(diphenylphosphino)ethylene (dppey) the copper(I) gold(I) complexes [M(dppey)2]PF6 has been carried out. complexes, which have shown to exhibit cytotoxic antitumour activity, belong relatively rare class with tetrahedral CuP4 AuP4 co-ordination spheres. Crystals dppey 1 are monoclinic space group P21/c a= 12.861(8), b= 13.097(2), c= 14.228(8)Å, β= 116.15(3)°; R was 0.047 for 3117 ‘observed’ reflections. CP MAS spectrum consists an AB multiplet δ(PA)–24.2, δ(PB)–27.2 J(P–P)= 126 Hz. [Cu(dppey)2]PF62 orthorhombic P212121 14.479(5), 16.703(4), 20.891(4)Å; 0.046 3138 sphere is regular within constraints chelation Cu–P in range 2.276(2)–2.289(2)Å. copper atom lies on a pseudo two-fold axis symmetry bisecting CC bonds. Charge-transfer interactions between phenyl rings each ligand contribute stabilization structure cation. four broad bands (Δν½= 300 Hz) centred at δ 8 J(Cu–P)≈ 820 Distortion quartet spacings by quadrupolar interaction nuclei minimal. [Au(dppey)2]PF63 isomorphous 2 14.644(4), 16.703(1), 20.699(5)Å; 0.025 3947 Au–P distances lie narrow 2.377(2)–2.388(2)Å. Solid-state this complex analogous nitrate chloride magnetic field strengths 2.11, 7.05 9.40 T reveal splitting phosphorus signal into ascribed spin–spin coupling effects J(Au–P) estimated be 200 As complex, distortion minimal indicative small 197Au constant. Solution chemical shift parameters similar, supporting hypothesis that bis(chelated) cations also stable solution. Spin–spin (197Au or 63/65Cu) not resolved solution spectra, however, due rapid relaxation.