Symmetrization of Phenylmercuric Hydroxides by the Action of Nickel(II) and Cobalt(II) Acetylacetonates. Isolation and Structural Characterization of an Intermediate in This Reaction

Abstract

The complex adducts [M(acac)2(PhHgOHgPh)]2 (M = Co, Ni) have been obtained by incorporation of PhHgOH into the coordination sphere of M(acac)2 at ambient temperature. The X-ray crystal structure of [Ni(acac)2(PhHgOHgPh)(Et2O)]2 (1c) reveals a dimeric nickel complex coordinated by the acetylacetonate oxygen and the bridging oxygen of bis(phenylmercuric) oxide. Refluxing a THF solution of compound 1c gave diphenylmercury, HgO, and Ni(acac)2(THF)2. With PhHgOH or PhHgSH the symmetrization reactions also occurred when catalytic amounts of Ni(acac)2 were used. In contrast, triphenyltin derivatives (hydroxide, acetate, oxide) on treatment with M(acac)2 in aqueous THF gave the stable complexes [M(acac)2(Ph3SnOH)]2 (M = Co, Ni). The structure of [Ni(acac)2(Ph3SnOH)]2 (2) was also determined by X-ray crystallography.

Bis(μ-acetylacetonato-κ2O:O′)bis[(acetylacetonato-κ2O,O′)aquanickel(II)] hemihydrate

“…The solid-state structure for octahedral complexes of the type [M(acac) 2 (L)] 2 (M = Ni, Co; acac = acetylacetonate; L = alcohols, amines) have recently been reported (Kessler et al, 2003;O'Connor et al, 1984;He, Yao, Luo, Zhang, Lui, Zhang & Wu, 2003;Doring et al 1997). Such complexes are potential precursors for chemical vapor deposition to form ceramic oxides, for example NiO, which is used in ceramic material applications.…”

An X-ray absorption spectroscopic study at the mercury LIII edge on phenylmercury(II) oxygen species

“…Bloodworth reports a true PhHgOH, which is dehydrated to a stable (PhHg) 2 O, based on spectroscopic and gravimetric data 5 . More recently Doring et al have demonstrated that Ni(acac) 2 catalyses the disproportionation reaction of PhHgOH to Ph 2 Hg, HgO and H 2 O, and they isolated a dimeric nickel complex with a bridging (PhHg) 2 O ligand which may be an intermediate in the process 6 .…”

Conformational Isomerism in Monomeric, Low‐Coordinate Group 12 Complexes Stabilized by a Naphthyl‐Substituted m‐Terphenyl Ligand

“…[20,50] The Hg À O distance for 3 is 3.019 (6) , which is shorter than that in (14) ]. [51] A survey of the literature reveals that 2 and 3 are rare examples of structurally authenticated Cd and Hg complexes to feature a diethyl ether molecule coordinated to the metal. [48,51] The two metal-substituted aryl rings are oriented at angles of 63.00(13)8 (2) and 62.1(3)8 (3) from each other.…”

“…[51] A survey of the literature reveals that 2 and 3 are rare examples of structurally authenticated Cd and Hg complexes to feature a diethyl ether molecule coordinated to the metal. [48,51] The two metal-substituted aryl rings are oriented at angles of 63.00(13)8 (2) and 62.1(3)8 (3) from each other. The terphenyl ligands in 2 and 3 are both arranged in a synconfiguration with all of the flanking naphthyls having their outer phenyl rings turned away from the metal.…”