21209-78-9Relevant articles and documents
Comparing Protonolysis and Transmetalation Reactions: Microcalorimetric Studies of C-AuI Bonds in [AuRL] Complexes
Pérez-Iglesias, María,Espinet, Pablo,Casares, Juan A.
, p. 11193 - 11200 (2018)
The protonolysis of C-Au bonds in [AuRL] organometallic complexes has been studied by calorimetry for 12 R groups. The experimental data have been combined with density functional theory calculations to obtain bond dissociation energy (BDE) values. The C-Au BDE values show a good correlation with the corresponding isolobal C-H BDE values. The heat released in the protonolysis of [AuRL] has also been measured for R = Ph and L = P(OPh)3, PPh3, PMe3, PCy3, and IPr, and these values strongly depend on the trans influence of L because of the mutual destabilization of the L-Au and Au-C bonds. The enthalpies of the transmetalation reaction [AuR(PPh3)] + SnIBu3 → [AuI(PPh3)] + SnRBu3 for seven R groups have been measured and compared with those of the corresponding [AuR(PPh3)] protonolysis.
Bridging phenyl ligands. Unsaturated mercury-triosmium carbonyl cluster complexes containing bridging phenyl ligands
Adams, Richard D.,Luo, Zhongwen,Wong, Yuen Onn
, p. 46 - 51 (2015)
Abstract The gold phosphine group in the complex Os3(CO)10(μ-η1-Ph)(μ-AuPPh3), 1 can be replaced by mercury halide groups by reactions with mercury halides. The reaction of 1 with HgI2 yielded the new
Studies of the structures and bonding of gold-bridged dirhenium carbonyl cluster complexes
Adams, Richard D.,Wong, Yuen Onn,Zhang, Qiang
, p. 7540 - 7546 (2014/04/03)
The compounds Re2(CO)8(μ-AuPPh3) 2, 1, a dimer of Re(CO)4(μ-AuPPh3), and ax,ax-Re2(CO)8(PPh3)2 were obtained from UV-vis radiation-induced decarbonylation of the compound Re(CO) 5[Au(PPh3)]. Compound 1 contains two rhenium atoms bridged by two AuPPh3 groups. The complex has 32 valence electrons and is formally unsaturated by the amount of two electrons. The Re-Re bond distance in 1 is unusually short (Re-Re = 2.9070(3) A), as found by a single-crystal structural analysis. The nature of the metal-metal bonding in 1 was investigated by DFT computational analyses, which have provided evidence not only for σ-bonding but also significant complementary π-bonding directly between the two rhenium atoms. The electronic structure of Re2(CO) 8(μ-H)2, 2, was similarly analyzed and is compared with that of 1. Compound 1 is intensely colored due to low-energy, metal-based electronic transitions between the HOMO and HOMO-2 and the LUMO. Compound 1 reacts with I2 to yield Re2(CO)8(μ- AuPPh3)(μ-I), 3, and the known compound Re2(CO) 8(μ-I)2, 4, by substitution of the bridging AuPPh 3 groups with bridging iodide ligands. Compound 3 is electronically saturated, 34 valence electrons, and contains a formal Re-Re single bond: Re-Re = 3.2067(5) A. Compound 3 was also in a high yield (83%) from the reaction of Re2(CO)8(μ-H)(μ-CH=CHC4H9) with Au(PPh3)I. The Re-Re bonding in compounds 3, 4, and Re 2(CO)10 was also analyzed computationally, and this bonding was compared with their bonding in 1 and 2.
