Structure and bonding in gold(I) compounds. Part 2. Mössbauer spectrum of linear gold(I) complexes

Abstract

Structure and Bonding in Gold(i) Compounds. Part 2.t Mossbauer Spectrum of Linear Gold([) Complexes

DFT Study of HFI in Halogen-Containing Gold, Silver and Copper Complexes

“…Moreover, it is especially important that the calculation of NQCC of gold nuclei with use ADF program as against B3LYP/SDD calculations are close experimental data ( for a non-relativistic basis set Probably not so high quality of (7) and (8) correlations (the large standard curve fit errors) is due to the great sensitivity of the EPG's to the size of the basis set especially in the core region [31] and to deficiencies in the exchange-correlation potential [32]. Table V presents the experimental values of the Mössbauer isomer shifts [2,11] and the calculated populations of the 6s-, 6p-and 5d-orbitals of gold atom from NBO approach. It is necessary to note, that the population of the 6p orbital of a gold atom is close to zero.…”

“…However, the comparison between QS and proton ability of complexes with ligands such as Cl j , CO and PPh 3 published by Jones et al [2] displayed an opposite trend. Besides, many results of the calculations of MXCO complexes show that the np orbital occupations are close to zero.…”

“…Structural data and vibrational frequencies were obtained with very good agreement with experimental data. A molecular orbital analysis shows that metal d-and metal pcontribution are important in metal ligand bonding in contrast to the interpretation of Mössbauer data [2]. Microwave spectra of the MXL (M = Au, Ag, Cu; X = Cl, Br; L = ligands) complexes and nuclear quadrupole coupling constants (NQCC) for Cu, Au, Br and CI nuclei of studied compounds were presented by Gerry and coworkers [3][4][5][6][7].…”

“…Two different bonding schemes have been proposed for such complexes [2]. The M + is formally nd 10 ion, and the simpler explanation supposes donation from the ligands into the empty 6s and 6p z orbitals of the metal atom (the z axis being the chlorine-metal-ligand axis).…”

Bis(tricyclohexylphosphine)gold(I) thiocyanate

“…The complexes Me2PhP, and Et2PhP, all fit the correlation for linear complexes but the trigonal complex [Au(PhaP)2C1] does not (McAuliffe, Parish & Randall, 1977). Similarly, the complexes [AuL 2] PF 6, for a wide variety of ligands including L = (C6Hll)3P as well as other phosphines, fit the correlation for linear complexes (Jones, Maddock, Mays, Muir & Williams, 1977), while [Au(PhaP)2(SCN)] was assigned as three coordinate (Jones, Jones, Maddock, Mays, Vergnano & Williams, 1977).…”