Structure and dynamic behavior of neutral hexacoordinate antimony compounds with intramolecular coordination

Abstract

Neutral hexacoordinate organoantimony compounds LSb(Xyl)C 6 H 4 (o-Y) [L

Synthesis, Structure and Applications of Hypervalent Organoantimony Compounds Having Intramolecular E→Sb (E = N, O, S) Coordinations

“…Yamamoto et al reported the first hypervalent organoantimony compound containing pendant-arm ligand 2-(Me 2 NCH 2 )C 6 H 4 in 1992 [40]. Almost all the hypervalent organoantimony compounds with intramolecular N Sb interaction reported so far are trivalent compounds, though a few pentavalent and monovalent compounds have also been reported [37,[41][42][43][44].…”

“…The structure, reactivity, and property of this kind of compounds have been widely investigated both experimentally and theoretically [29][30][31][32][33]. The outcome enables us to know more about the nature of hypervalent organoantimony compounds, especially those with intramolecular N, O, S Sb coordinations [34][35][36][37][38][39]. In the monograph edited by Akiba in 1999 on hypervalent compounds, the static and dynamic structures of hypervalent Sb (III) halides were only briefly presented (by Yamada and Okuda) [33].…”

Synthesis and structure of N,C-chelated organoantimony(v) and organobismuth(v) compounds

“…8 Several organopnictogen(V) compounds bearing a tridentate ligand are known as well. 9 For example, compound RSb(C 6 H 6 -3,5-Me 2 )Cl (R = CF 3 C(2-C 6 H 4 ) 2 O) reacts with R′Li (R′ = 2-(Me 2 NCH 2 )C 6 H 4 , 2-(2-Py)C 6 H 4 ) with formation of N,C-chelated antimony(V) compounds. 9 Oxidation of MeN(CH 2 C 6 H 4 ) 2 Sb(C 6 H 4 -4-Me) using SO 2 Cl 2 or Br 2 gave the corresponding dihalides MeN-(CH 2 C 6 H 4 ) 2 Sb(C 6 H 4 -4-Me)X 2 (X = Cl, Br) and conversion of the chloride with KF gave the corresponding fluoride MeN-(CH 2 C 6 H 4 ) 2 Sb(C 6 H 4 -4-Me)F 2 .…”

“…9 For example, compound RSb(C 6 H 6 -3,5-Me 2 )Cl (R = CF 3 C(2-C 6 H 4 ) 2 O) reacts with R′Li (R′ = 2-(Me 2 NCH 2 )C 6 H 4 , 2-(2-Py)C 6 H 4 ) with formation of N,C-chelated antimony(V) compounds. 9 Oxidation of MeN(CH 2 C 6 H 4 ) 2 Sb(C 6 H 4 -4-Me) using SO 2 Cl 2 or Br 2 gave the corresponding dihalides MeN-(CH 2 C 6 H 4 ) 2 Sb(C 6 H 4 -4-Me)X 2 (X = Cl, Br) and conversion of the chloride with KF gave the corresponding fluoride MeN-(CH 2 C 6 H 4 ) 2 Sb(C 6 H 4 -4-Me)F 2 . 10 10 Recently, we 11 and the Mehring group 12 have introduced a new N,C-chelating ligand L (L = [o-(CHvN-2,6-iPr 2 C 6 H 3 )C 6 H 4 ]) to the chemistry of heavier group 15 elements.…”

“…In order to test the possibility of stabilization of antimony(V) and bismuth(V) compounds by the ligand L and to further develop the knowledge about this class of compounds, we report here the oxidation of compounds LMCl 2 (M = Sb (1) or Bi (2)), LM(Ph)Cl (M = Sb (3) or Bi (4)) and LMPh 2 (M = Sb (5) or Bi ( 6)). These reactions afforded a set of pentavalent compounds LSbCl 4 (7), LSb(Ph)Cl 3 (8), LSbPh 2 Cl 2 (9), LBi(Ph)Cl 3 (10) and LBiPh 2 Cl 2 (11) that were characterized by elemental analysis, ESI-mass spectrometry, and 1 H and 13 C NMR spectroscopy and the molecular structures of compounds 3-7, 9 and 11 were unambiguously established using single-crystal X-ray diffraction analysis.…”