STEREOCHEMISTRY OF ADAMANTANOID [μ-SPh)6(CdCl)4]2- ANIONS

Abstract

The crystal and molecular structures of compounds (Cat>2[Cd 4^-SPh) 6 Cl 4 ] (Cat = Et^N^.l; Pr^N 4 ". 2; Bu^N", 3) have been determined by single crystal X-ray (Effraction techniques to study the influence of the cations on the stereochemistry and configurational isomerism of the [Cd 4^-SPh) 6 Cl 4 ] 2 " anions. The results of our investigation show that the cations have profound effect on the crystal and molecular structures including the orientation of phenyl rings along the S-C axes, but do not change the configuration of the substituents, i.e., the phenyl rings of the thiolate ligands. In each anion, the configuration (axial or equatorial) of the phenyl groups in the four six-membered rings is [aae, aae, aee, aee], corresponding to isomer III.

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

“…H5hpdta, Fe(NO3)3, en, dma / H2O, 3 days K [139] [{Fe2(bpbp)}2O2(OH)2](ClO4)4 (220) Hbpbp, Fe(ClO4)3 / THF, H2O, RT, 2 days I [140] [(Fe2{(TACN)CH2}2CHOH)O(OH)]2[PF6]4 (221) {(TACN)CH2}2CHOH , FeCl3, NaOAc, NEt3, K[PF6] / i PrOH, 24-36 h K [141] [Fe4(N-Et-HPTB)2O4][BF4]2 (222) [Fe2(N-Et-HPTB)(dmf)4][BF4]3, O2 / DMF K [142] [{Fe( t BuOH)}4(dppoe)4(OH)6][PF6]2Cl4 (223) [closo-1,12-C2B11H10(CN)2], [(Cp)(dppe)FeCl], [NH]4[PF6], t BuOH / THF, 66 °C, 18 h J [143] [{Fe(TACN)}4O2(OH)4]X4 (224-225, X = I, CIO4) NaX, [(TACN)2Fe2(acac)2(O)](ClO4)2 / Me2CO, H2O, 2 weeks I [144] [{Fe(TACN)}4O(OH)5](I)4I3 (226) [(TACN)FeCl3], KI / H2O, Py, 72 h D [145] [{Fe(TACN)}4O2(OH)]Br4 (227) [(TACN)FeCl3], NaBr / H2O, 25 °C, pH = 10.28 D [146]…”

“…This can be done by ligand exchange reactions with PhICl2, Br2 or I2, [214,224] or during cluster formation by using halide salts, which can also be used to stabilize Hg clusters including rare examples of Hg4Te6 scaffolds. [225][226][227][228][229][230] As described for the pure chalcogenolate clusters, mixed metal adamantanes [Et4N]2[(MI)4(M´I)4-n(S n Pr)6] (434-442, M = Zn, Cd, Hg, Figure 10) can be obtained by exchange reactions between homometallic congeners. Asymmetric substitution at the terminal position is possible as well.…”

“…This can be done by ligand exchange reactions with PhICl 2 , Br 2 or I 2 , 214,224 or during cluster formation by using halide salts, which can also be used to stabilize Hg clusters including rare examples of Hg 4 Te 6 scaffolds. 225–230…”