Structural, (197)Au Mössbauer and solid state (31)P CP/MAS NMR studies on bis (cis-bis(diphenylphosphino)ethylene) gold(I) complexes [Au(dppey)(2)]X for X = PF(6), I.
(197)Au Mössbauer spectra for the d(10) gold(i) phosphine complexes, [Au(dppey)(2)]X (X = PF(6), I; dppey = (cis-bis(diphenylphosphino)ethylene), and the single crystal X-ray structure and solid state (31)P CPMAS NMR spectrum of [Au(dppey)(2)]I are reported here. In [Au(dppey)(2)]I the AuP(4) coordination geometry is distorted from the approximately D(2) symmetry observed for the PF(6)(-) complex with Au-P bond lengths 2.380(2)-2.426(2) A and inter-ligand P-Au-P angles 110.63(5)-137.71(8) degrees . Quadrupole splitting parameters derived from the Mössbauer spectra are consistent with the increased distortion of the AuP(4) coordination sphere with values of 1.22 and 1.46 mm s(-1) for the PF(6)(-) and I(-) complexes respectively. In the solid state (31)P CP MAS NMR spectrum of [Au(dppey)(2)]I, signals for each of the four crystallographically independent phosphorus nuclei are observed, with the magnitude of the (197)Au quadrupole coupling being sufficiently large to produce a collapse of (1)J(Au-P) splitting from quartets to doublets. The results highlight the important role played by the counter anion in the determination of the structural and spectroscopic properties of these sterically crowded d(10) complexes.
Healy
Peter C
PC
School of Biomolecular and Physical Sciences, Griffith University, Nathan, Queensland, Australia 4111.
Loughrey
Bradley T
BT
Bowmaker
Graham A
GA
Hanna
John V
JV
D018360:Crystallography, X-Ray; D006046:Gold / Q000737:chemistry*; D007454:Iodides / Q000737:chemistry; D009682:Magnetic Resonance Spectroscopy / Q000379:methods*; D009942:Organometallic Compounds / Q000737:chemistry*; D015204:Spectroscopy, Mossbauer / Q000379:methods*
D007454:Iodides; D009942:Organometallic Compounds; D006046:Gold