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

Abstract

The CdS3 skeleton of the anion in monoclinic (Ph4P)[Cd(S{O}CPh)3] has a near-planar structure, but among the three crystallographically different anions in the structure of rhombohedral (Ph4P)[Cd(S{O}CPh)3] there are both planar and uniquely pyramidal CdS3 skeletons. Thus, the [Cd(S{O}CPh)3]- anion provides a new example of polytopal isomerism.

Thioacetate complexes of Group 12 metals. Structures of [Ph4P][Zn(SC{O}Me)3(H2O)] and [Ph4P][Cd(SC{O}Me)3] †

“…The disposition of the three carbonyl groups on the opposite side of the Cd to the S 3 plane results in the anion having a propellerlike geometry with an approximate C 3 point group symmetry, as found also for thiobenzoate complexes of Co, Ni and Mn, 1 and the type A and C anions of rhombohedral [Ph 4 P][Cd-(SC{O}Ph) 3 ]. 9 Overall, the geometry is most reminiscent of that of the type C anions in rhombohedral [Ph 4 P][Cd(SC{O}Ph) 3 ]. 9 It is interesting that the compound 2 has crystallised in a polar space group (P2 1 ) as observed for the thiobenzoate complexes having (some) anions with fac geometry.…”

“…9 Overall, the geometry is most reminiscent of that of the type C anions in rhombohedral [Ph 4 P][Cd(SC{O}Ph) 3 ]. 9 It is interesting that the compound 2 has crystallised in a polar space group (P2 1 ) as observed for the thiobenzoate complexes having (some) anions with fac geometry. 18 The Cd ؒ ؒ ؒ O distances of [Cd(SC{O}Me) 3 ] Ϫ are less than the sum of the van der Waals radii, 3.10 Å.…”

“…[11][12][13][14][15][16] Rhombohedral [Ph 4 P][Cd(SC-{O}Ph) 3 ] has a unique structure containing both planar and pyramidal CdS 3 kernels. 9 Unlike those of [M(SC{O}Ph) 3 ] Ϫ (M = Mn, Co or Ni), the pyramidal MS 3 kernels in the rhombohedral salt exhibit only weak M ؒ ؒ ؒ O interactions.…”

“…For the past several years we have been interested in the chemistry of thiobenzoates. [1][2][3][4][5][6][7][8][9][10] The presence of both hard and soft donor sites makes thiocarboxylates, RC{O}S Ϫ in general, interesting ligands. Recently, we have reported 1 homoleptic anionic complexes [M(SC{O}Ph) 3 ] Ϫ (M = Mn, Co or Ni) in which both oxygen and sulfur atoms of the thiobenzoate ligands are bonded to the central metal atom in a bidentate fashion.…”

Chemistry of thiocarboxylates: syntheses and characterization of silver and copper thiocarboxylate complexes, and the structures of [Ph4P][M(SC{O}Me)2] (M = Cu or Ag) and [Et3NH][Ag(SC{O}Ph)2]

“…2 We have been interested in the chemistry of the thiobenzoate anion. [3][4][5][6][7][8][9][10][11][12] In most † [M(SC{O}Ph) 3 ] Ϫ anions of the Group 12 elements, the metal atoms are surrounded by three sulfur atoms in a trigonal planar fashion. 3 This unusual geometry is otherwise exhibited only in complexes of bulky thiolate ligands.…”