Metal-thiolate chemistry: The structure of the first adamantane-type cation, [(μ-SPh)₆(HgPPh₃)₄]²⁺

Abstract

The compound [(p-SC6H5)6{HgP(C6H5)3}4][C104]2 crystallizes in the $clinic space group pi as a bis(ch1oroform) solvate with cell dimensions a = 15.799(4), b = 26.813(5), c = 15.040(5) A, a = 96.35(2), P = 114.52(2), y = 100.45(2)" and two formula units per cell. The crystal and molecular structures of this salt were solved by X-ray diffraction techniques using 9898 counter data with I > 2.5a(I) recorded at -50(2)"C. Refinement of 477 variables by full-matrix leastsquares converged at an agreement factor R = 0.046. The cation has adarnantane-type stereochemistry with a (p-SPh)&g, cage and four terminal triphenylphosphine ligands. The S-C, vectors of the bridging SC6H5 groups adopt the configuration [aae, aae, aee, aee] with the minimum number of two 1,3-axial, axial substituent interactions. There is a significant flattening of the two Hg3S, rings with two axial substituents into an envelope conformation; each has two torsion angles less than 25", instead of the ideal values of 260" in adamantane. One perchlorate ion is doubly solvated by chloroform molecules in an unusual, weakly hydrogen bonded, [C104. 2HCC13]-complex.

Structure-Directing Influence of Halide in Mercury Thiolate Clusters

“…8 Such a variation is commonly found for terminal and bridging Hg-Br distances of thiolate-bridged compounds of Hg(II). 48 The Hg-Br-Hg bridge is symmetrical (3.073(11) Å), which is in contrast to the fact that unsymmetrical Hg-Br-Hg bridges are more frequently observed. 13, [49][50][51][52] The weak Hg-S br (between units) and normal Hg-Br br distances suggest that Br plays a more important role than S in holding the three different units together.…”

Adamantane-type clusters: compounds with a ubiquitous architecture but a wide variety of compositions and unexpected materials properties

“…[233,234] A complex precursor [M(L)2(ClO4)2] (M = Cd, Hg; L = PPh3, PEt3, AsPh3) in combination with M(ER)2 (E = S, Se) and free L leads to cationic clusters in [(ML)4(ER)6][ClO4]2 (453-464, Figure 10). [235][236][237] With certain L and R combinations, this can lead to clusters with a few terminally uncoordinated M sites, which do not, however, influence the charge. [235] There are only two examples with oxygen in the E position.…”

“…[Hg(PPh3)2(ClO4)2], Hg(EPh)2, PPh3 / CHCl3, 10 min C [236,237] [(HgPPh3)4(SMe)6][ClO4]2 (457) [Hg(PPh3)2(ClO4)2], Hg(SMe)2, PPh3 / CHCl3, 10 min C [236] [(HgPPh3)4(SEt)6][ClO4]2 (458) [Hg(PPh3)2(ClO4)2], Hg(SEt)2, PPh3 / CH2Cl2, 10 min C [236] [(HgAsPh3)4(SPh)6][ClO4]2 (459) [Hg(AsPh3)2(ClO4)2], Hg(SPh)2, AsPh3 / CHCl3, 10 min C [236] [(HgPEt3)4(SPh)6][ClO4]2 (460) [Hg(PEt3)2(ClO4)2], Hg(SPh)2, PEt3 / Me2CO C [236] [(HgPEt3)4(SePh)6][ClO4]2 (461) [Hg(PEt3)2(ClO4)2], Hg(SePh)2, PEt3 / CHCl3, 10 min C [236] [Cd(CdPPh3)3(S n Pr)6][ClO4]2 (462) [Cd(PPh3)2(ClO4)2], Cd(S n Pr)2, PPh3 / CH2Cl2, 20 min C [235]…”

“…10). [235][236][237] With certain L and R combinations, this can lead to clusters with a few terminally uncoordinated M sites, which do not, however, inuence the charge. 235 There are only two examples with oxygen in the E position.…”