Determination of the molecular structure and absolute configuration of (R)-tris(trifluoroacetato)antimony(III)

Intramolecularly coordinated organoantimony(III) carboxylates

“…Organoantimony(III) carboxylates characterized in the solid state by the XRD method include Sb(OOCCH 3 ) 3 [7], Sb(OOCCH 2 CH 3 ) 3 [8], Sb(OOCCF 3 ) 3 [9] and SbPh 2 (OOCCH 3 ), that forms polymeric chains in the solid state through acetate bridges [10]. The phthalic acid was used as a bridging ligand between two antimony centres as well [11].…”

Multiply bridged organodiantimony(V) compounds; crystal structures of [(SbR2)2(μ-O)2(μ -O2AsMe2)2] (R = Ph or p-tolyl) and [(SbR3)2(μ-O)(μ-O2 MR′2)2] (R = Ph, M = P, R′ = Me; R = Ph, M = As, R′ = Me or Ph; R = p-tolyl, M = P, R′ = Me)

“…Crystal structures for both [(SbCl 3 ) 2 (µ-O)(µ-O 2 PMe 2 ) 2 ] and [(SbPh 2 Cl) 2 (µ-O){µ-O 2 P(C 6 H 11 ) 2 } 2 ] show octahedral coordination at antimony with bidentate phosphinate groups; the geometry is similar in the related carboxylate-bridged compound [(SbF 3 ) 2 (µ-O)(µ-O 2 CCF 3 ) 2 ]. 17 Phosphinates and arsinates can, however, behave as either unidentate or chelating ligands and the work described in this paper was carried out to define further the conditions under which the groups might bridge between pairs of antimony atoms already linked by either one or two oxygen atoms. The starting materials were the singly bridged dihalides [(SbR 3 X) 2 O], where X = Br or Cl and R = phenyl, p-tolyl or methyl, and the double bridged analogues [(SbR 2 BrO) 2 ] where R = phenyl or p-tolyl.…”

Influence of Internal Angular Arrangement on Pnicogen Bond Strength

“…This decrease in θ is nearly 20° for ZBi, and it diminishes down to only 2° for P. The rings are smaller within the Bi­(OCH 2 ) 3 CH cage in Figure c, so a certain degree of deformation is plausible, although this strain is small, increasing θ by less than 5° according to Table . In order to simulate numerous pnicogen-containing systems in the literature, which are more highly pyramidal, − the methylene groups were removed, as in Figure d, leading to shorter 3-atom Z–O–C chains. This greater strain increases the θ umbrella angle by some 15°, as indicated in the final column of Table , and an associated 25° decrease in the internal α angle.…”

“…A diffraction study of a molecule very much akin to P(OCH 2 ) 3 CH yielded an internal α angle of 101°, within 2° of the value computed here. The ZO 3 CH molecules with their higher degree of pyramidality model a number of systems in the literature, spanning all of the pnicogen atoms from P to Bi, with the Z connected to either O or N atoms. − The internal α angles of these units are as small as 80°, comparable to the optimized values for the ZO 3 CH systems examined here.…”