Synthesis, Spectral Characterization and Crystals Structure of some Arsane Derivatives of Gold (I) Complexes: A Comparative Density Functional Theory Study

Abstract

A series of complexes of the type LAuCl where L = tris(p-tolylarsane), tris(m-tolylarsane), bis(diphenylarsano)ethane, and tris(naphthyl)arsane have been synthesized. All of the new complexes, 1-4, have been fully characterized by means of 1H NMR and 13C NMR spectroscopy and single crystal X-ray crystallography. The structures of complexes 1-4 have been determined from X-ray diffraction data. The linear molecules have an average bond distance between gold-arsenic and gold-chlorine of 2.3390Å and 2.2846Å, respectively. Aurophilic interaction was prominent in complex 1 and 3, whereas complex 2 and 4 do not show any such interaction. The intermolecular gold interaction bond length was affected by the electronegativity of the molecule. The computed values calculated at DFT level using B3LYP function are in good agreement with the experimental results.

Buchwald‐Type Ligands on Gold(I) Catalysis

“…The structure of the As‐based dialkyl‐biphenyl gold(I) complexes are in line with what already reported for other As based gold(I) complexes . Compared to the phosphorous analogous, the Au−Cl or Au−N distance is shorter, in line with the expected increased electrophilicity of the complexes.…”

Unsymmetrical Coordination of Bipyridine in Three-Coordinate Gold(I) Complexes

“…The hypothetical 1′ was found to have a distorted geometry with the gold center bending 10.36° away from the plane of the uncoordinated pyridine ring. The Au–N1 and Au–P bond distances in 1 were slightly overestimated by the calculations, Table , as is common for DFT results. − The Au–N2 distance in 1 was ∼0.019 Å shorter than expected, most likely due to the overestimation of the stronger Au–P bond. Frequency calculations indicate that 1 , 1′ , 2 , and 2′ occupy local minima, whereas 3 ‡ was found to have one imaginary frequency corresponding to an asymmetric distortion of the two Au–N bonds.…”