Three-coordinate thiolato complexes of zinc: solution and solid-state structures and EHMO analysis of the bonding pattern of [Zn(S-tert-Bu3C6H2-2,4,6)2]2

Abstract

The volatile zinc thiolato complex Zn(SAr")2 (1) (Ar" = C6H2-f-Bu3-2,4,6) was characterized by variable-temperature and solid-state 13C CP-MAS NMR and X-ray crystallography. The compound is dimeric in the solid state, with trigonal-planar zinc coordinated to three sulfur ligands and asymmetric thiolato bridges. In benzene solution, 1 dissociates into two-coordinate monomers, while at low temperature dimeric species exist in dichloromethane or toluene. The skeletal bonding pattern and the asymmetry of the thiolato bridges are explained on the basis of EHMO calculations; the Zn-S bonds are essentially a in character, with negligible contributions from Zn-S (p-p)T interactions. Crystal data for 1: triclinic space group ; Z = 2; a = 10.333( 5), b -11.226( 9), c = 32.266(30) A; a = 81.29(2), ß = 86.12(2), y = 86.07(2)°; V= 3684.70 A1 23; R = 0.059, Re = 0.068 based on 4519 reflections with F0 > 2<r(F0).

Synthesis and Structural Characterization of Neutral Silver(I) Complexes with Arenephosphinothiols. Crystal Structures of [Ag4{2-(Ph2P)-6-(Me3Si)C6H6S}4] and [Ag4{2-(Ph2PO)-6-(Me3Si)C6H3S}4]

“…Thus, for example, the crystal structure of [M(SPh) 2 ] (M = Zn or Cd), with SPh - ligands, which may be regarded as prototypes for sterically less hindered ligands, are polynuclear. However, the presence of a methyl group in the ortho position on the phenyl ring gives a heptanuclear cadmium complex, and the presence of three bulkier tert -butyl groups in the ring allows the formation of binuclear compounds [M(SC 6 H 2 tBu 3 -2,4,6) 2 ] 2 (M = Zn or Cd). A similar situation is found in the silver chemistry.…”

Polytopal Isomerism of the [Cd(S{O}CPh)3]-Anion

“…An intriguing feature of the structures has been the occurrence and planarity, or near-planarity, of the MS 3 skeleton. For the divalent zinc group elements, clear MS 3 skeletons have otherwise been found only in thiolate complexes, usually with sterically hindered thiolates. − In these complexes, the skeletons are (near-)planar also.…”

Tetrakis(μ-triisopropylsilanethiolato)-1:2κ4S:S;2:3κ4S:S-bis(triisopropylsilanethiolato)-1κS,3κS-trizinc(II)

“…The structure type observed for (I) also does not appear to have a precedent within the larger body of structurally authenticated homoleptic alkanethiolate complexes of Zn. This larger set of complexes includes two- (Nguyen et al, 2005;Ellison & Power, 1994), three- (Gruff & Koch, 1989;Matsunaga et al, 2005) and four-coordinate mononuclear zinc thiolates (Ueyama et al, 1988;Silver et al, 1993), three- (Grü tzmacher et al, 1992;Bochmann et al, 1993) and fourcoordinate dinuclear Zn thiolates (Watson et al, 1985;Abrahams et al, 1987;Gelinsky & Vahrenkamp, 2002) and adamantanoid-type tetranuclear anions with tetrahedral coordination at zinc (Hencher et al, 1985;Gelinsky & Vahrenkamp, 2002), but no species with mixed coordination numbers at the metal. The closest analogs to compound (I), showing coordination numbers of both three and four, are the arenethiolate complexes [(2,6-i Pr 2 C 6 H 3 S)E(-2,6-i Pr 2 C 6 H 3 -S) 2 E(-2,6-i Pr 2 C 6 H 3 S) 2 E(2,6-i Pr 2 C 6 H 3 S)] (E = Sn or Pb) (Hitchcock et al, 1983).…”