Reactivity of [M(C∧P)(acac-O,O‘)] [M = Pt, Pd; C∧P = CH₂-C₆H₄-P(o-tolyl)₂-κC,P; acac = 2,4-pentanedionato] toward HgX₂ (X = Br, I, CH₃COO, CF₃COO). New Polynuclear Complexes Containing Pt−Hg Bonds. Molecular Structures of [{Pt(C∧P)(acac-O,O‘)- HgBr(μ-Br)}₂(μ-HgBr₂)], an Unprecedented Square-Planar Bromomercurate Complex, and [{Pt(C∧P)(μ-O₂CCH₃)₂Hg(μ³-acac

Abstract

The complexes [M(C∧P)(acac-O,O′)] [M ) Pt ( 1) Pd (1′); C∧P ) CH 2 -C 6 H 4 -P(o-tolyl) 2 -κC,P; acac ) 2,4-pentanedionato] were prepared by the reaction of [M(C∧P)(µ-Cl)] 2 [M ) Pt, Pd] with Tl(acac) and fully characterized. The reactions of [Pt(C∧P)(acac-O,O′)] (1) with equimolar amounts of HgX 2 (X ) I, Br) give the polynuclear complexes [Pt(C∧P)(acac-O,O′)HgI(µ-I)] 2 (2) and [{Pt(C∧P)(acac-O,O′)HgBr(µ-Br)} 2 (µ-HgBr 2 )] ( 3) containing unsupported Pt-to-Hg donor bonds. In the pentanuclear complex 3, the central mercury atom shows an unexpected square-planar environment, unprecedented for halomercurates(II). The complex [Pt(C∧P)-(acac-O,O′)] (1) also reacts with Hg(O 2 CR) 2 (R ) CH 3 , CF 3 ), but in 1:2 molar ratio, to afford the neutral hexanuclear complexes [Pt(C∧P)(µ-O 2 CR) 2 Hg(µ 3 -acac 2--κC 3 ,O)Hg(O 2 CR-κO)] 2 [R ) CH 3 (4), CF 3 (5)]. An X-ray study of 4 revealed that these compounds contain very short platinum-to-mercury donor bonds supported by two carboxylate groups, along with an unusual dimercurated acetylacetone moiety. The reactions of [Pd(C∧P)(acac-O,O′)] (1′) with HgX 2 (X ) Br, I, CH 3 COO, CF 3 COO) proceed mainly (X ) Br, CH 3 COO, CF 3 COO) with substitution of the acac-O,O′ ligand by X from the coordination environment of the palladium center to give the binuclear derivatives [Pd(C∧P)(µ-X)] 2 (X ) Br, CH 3 COO, CF 3 COO), hindering the obtention of palladium-mercury compounds by this route.

An Extended Chain and Trinuclear Complexes Based on Pt(II)–M (M = Tl(I), Pb(II)) Bonds: Contrasting Photophysical Behavior

“…[44][45][46][47][48] Within this area, a great number of systems stabilized by donor-acceptor Pt→M' bonds have been reported. [12][13][14][15][16][17][21][22][23][24]26,27,30,[49][50][51][52][53][54][55][56][57][58][59][60][61][62][63][64][65] Among the acceptors M', configuration d 10 is the most widely represented, specially Ag(I) and, to a much lesser extent, Au(I), Hg(II) and Cd(II). In contrast to these Pt(d 8 configurations have been reported, including di (PtTl), 21,50,[66][67][68] tri (PtTl 2 , [69][70][71][72] Pt 2 Tl, 16,56,…”

Crystal structure of tetraiodobis[μ-(1,1′-(1,5-pentanediyl)-bis-1H-benzimidazole)]dimercury(II), [HgI2(C19H20N4)]2

“…In the search for supramolecular coordination networks with intriguing architectures and topologies, amarked increase in both interest and research activity has been given to extended solids of metals with d 10 configuration involving mercury because of their various coordination configurations and coordination numbers [1][2][3]. Especially some mercury(II) iodide complexes often behave differently compared with the chloride and bromide complexes.…”

“…Especially some mercury(II) iodide complexes often behave differently compared with the chloride and bromide complexes. Such as in thes eries HgX 2 (pyridine) 2 ,t he chloro derivative possesses an octahedral, halide-bridged polymeric structure, but the bromo and iodo derivativesa re monomeric [4,5]. In thesecomplexes,the mercurytypically hasalower coordinationnumberoffour.…”

First Report on Crystal Engineering of Hg(II) Halides with Fully Substituted 3,4-Pyridinedicarboxamides: Generation of Two-Dimensional Coordination Polymers and Linear Zig-Zag Chains of Mercury Metal Ions

“…Though Hg···Hg distance as short as 3.41Å has never been reported but many halide bridged Hg based structures, with ubiquitous Hg 2 X 2 bridges are known to have Hg···Hg inetarctions within this range. [133][134][135][136][137][138][139][140] However, compounds with these interactions leading to linear metal chains are rather rare. Lu et al, 141 (Table 2) parallel to the a axis.…”