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

Abstract

The reaction of N,C-intramolecularly coordinated organoantimony(iii) and organobismuth(iii) compounds LMCl2 (M = Sb () or Bi () and L = [o-(CH[double bond, length as m-dash]N-2,6-iPr2C6H3)C6H4]) with phenyllithium in a 1 : 1 or 1 : 2 molar ratio gave compounds LM(Ph)Cl (M = Sb () or Bi ()) and LMPh2 (M = Sb () or Bi ()) in moderate to good yields. Compound could also be prepared by the treatment of the lithium compound LLi with in situ prepared PhSbCl2. Oxidation of the antimony(iii) compounds , and with one equivalent of SO2Cl2 proceeded smoothly with formation of organoantimony(v) compounds LSbCl4 (), LSb(Ph)Cl3 () and LSbPh2Cl2 () in nearly quantitative yields. Compounds are yellowish solids that are stable for a long time even in the presence of air. In contrast, only organobismuth(iii) compounds and could be successfully oxidized using SO2Cl2 to give compounds LBi(Ph)Cl3 () and LBiPh2Cl2 (). Compound is stable, but compound readily decomposed in solution and could not be isolated and stored for a longer period. All attempts to prepare compound LBiCl4 by the oxidation of with SO2Cl2 failed and resulted only in a mixture of products. All studied compounds were characterized by electrospray ionization (ESI) mass spectrometry, and (1)H and (13)C NMR spectroscopy. The molecular structures of , and were unambiguously established using single-crystal X-ray diffraction analysis.

Intramolecularly Coordinated 2‐Iminomethylphenyltellurium Compounds

“…This lengthy route is probably the reason why 2‐iminomethylphenyltellurium species ( VI ) are less frequently described in the literature than other intramolecularly coordinated tellurium compounds ( I – V ) that are more readily available. Recently, 2‐iminomethylphenyl‐supported compounds of group 13, group 14, group 15, and the lighter group 16 elements, were prepared by the ortho ‐directed lithiation route, which prompted us to develop similar synthetic protocols also for tellurium species containing 2‐( tert ‐butyliminomethyl)phenyl‐ and 2‐(2′,6′‐diisopropylphenyliminomethyl)phenyltellurium species ( VI , Scheme ). Five archetypal tellurium compounds were prepared and fully characterized by heteronuclear NMR spectroscopy and X‐ray crystallography.…”

Organic Compounds of Bismuth: Synthesis, Structure, and Applications

“…The organobismuth compounds with the N,C-aryl ligand LBi(Ph)Cl and LMPh 2 were synthesized in high yields from aryllithium dichloride LBiCl 2 (L = o-(СH=N-Dipp)C 6 H 4 ) and phenyllithium in a ratio of 1 : 1 or 1 : 2 (Scheme 10) [11]. Li, respectively, at the 1 : 2 molar ratio [12].…”

“…Bromides R(C 6 F 5 )BiBr, R(Mes)BiBr, and R(Ph)-BiBr (R = 2-(Me 2 NCH 2 )C 6 H 4 ) were synthesized similarly from equimolar amounts of RBi-Br 2 and C 6 F 5 MgBr, MesMgBr, or PhMgBr or from PhBiBr 2 and RLi in a molar ratio of 1 : 1 (Scheme 89) [12]. In the monochlorides, one nitrogen atom is strongly coordinated to the bismuth atom (2.660 (11) The reactions of organobismuth(III) chlorides R 2 BiCl and RBiCl 2 , where R = 2-(Me 2 NCH 2 )C 6 H 4 , with alkaline metal pseudohalides in a molar ratio of 1 : 1 and 1 : 2, respectively, afforded hypervalent bismuth compounds R 2 BiX (X = NCO, SeCN) and RBiX 2 (X = NCO, NCS, and SeCN) (Scheme 95) [98].…”

Organobismuth Reagents: Synthesis, Properties and Applications in Organic Synthesis

“…77c, 79,80,153 Gabbaï demonstrated that bismuth can also act as a σ-acceptor with gold, resulting in the formation of hypervalent interactions, as illustrated in compound II. 156 The strong propensity of triarylbismuth compounds to form hypervalent interactions was demonstrated by Mehring in 2009 with tribenzylbismuthine VII where a Bi•••arene π-interaction was observed. 157 The formation of these secondary intermolecular interactions was explained by the donation of the π-aromatic system into Bi-C σ* orbitals.…”