Group V Arsenic, Antimony, and Bismuth

Crystal structures of pseudo-tiigonal-bipynunidal (9 X=OMe, R=44e X=NM, R=H) and the barriers to inversion in solution (using NMR spectroscoi ) have been detenraned.  

As slmwn by an dectran diffraction study, the azide groq in (C 3)2AsN3 (C5 symmetry) is irons to the CAsC bisector. Reaction of Ar2As (ArOSiMe3 (obtained from At2AsG and 

LiN(Ar )SiMe3) with Br2 provides o BrAr2As (M,-NAr )2As Ar2Br fonnation of (R R2As)2NR and R R2AsNHBu (R Ar, R2=aryl or alkyl R=Me or Et) has also been reported. Thermally- 

Electronic structure calculations have been carried out on organobismuth species [C4H4Bi-, C4H4Bi, C4H4BiH and (C4H4Bi)2] using effective core potentials and relativistically parametrized semi-empiral M.O. methods. Calculations (at the PM3 SCF level) have also been made on the molecular and electronic structures of neutral, cationic and anionic methyl-arsines, -stibines and -bismuthines.  

The isomerisation of (1) to (2) has been investigated crystal structures of both (1) and (2) have been determined.  

The reaction of 2,2 -dilithio-l,l -biiu hlhyl with RASCI2 (R=Me or Ph) provided the corresponding (+)-7-R-ditiaphtho[2,1 -fe 1, 2 -d]arsoles [ (6)]. The molecules are fluxional in solution with barriers between the conformational isomers (atropisomers) of 6S 1 (R=Me) and 60 1 kcal mof (R=Ph). An X-ray diffiaction study of [(5 - (6, R=Ph)], vdiich crystallized out by spontaneous resolution, revealed appreciable bending of the distorted luqshthyl residues away from each other.  

Thermolytic studies have been reported for (i) the 3-arsolenes, PhAsCH2CR=CR CH2 (which gave at 500 C (PhAs) and H2C=CRCR =CH2 (RJl-H, Me), (u) Bu Me2Sb 

Crystal structures have been determined for (i) [PhBiCl2(THF)], a Cl bridged polymer with square pyramidal Bi apical Ph base positions occupied by 1 terminal Cl, 2 bridging Cl and 

Chemical properties of di-coordlnate arsenic c aq oiinds have been reviewed. Reaction of (1, RjAs-Y Y=C1, Ph or R As) with Ll/TMED produces ij -RjAs-LITMED (2.). Successive treatment of ( ) with Li and FeClj gave (j ) in 

Thermal decomposition of MesAs (on a GaAs surface) and EtjjAsH, (n 0-3) have been studied absorption and decomposition of EtjAsH on silicon (100) surfaces have been Investigated by electron energy loss spectroscopy. Photolysis and plasma-assisted decomposition of MejAs have also attracted attention, as have the thermolyses of RjSb (R Me, Pr, CHj-CH and CH =CHCH2). 

Reactions and syntheses of Ph Bi(CF3)(5 n=l or 2), obtained from PhgBiX) and Cd(CFj)x.2MeCN have been studied ( ) decomposes in air and undergoes dlsmutatlon in solution. Synthesis and spectra have been reported for (1) Ar BKCaCR) 3 q (n=l or 2), and (ii) monomeric [2,4,6- 

Crystal structure determination of PhjSbSCN revealed 3 distinct trigonal 

PhiSbOCHeCH-CMeHR and (Iv) (10) and related species (obtained from 

A volume in the Patai s series, Chemistry of the Functional Groups , devoted to organo-arsenic, -antimony and -bismuth chemistry, has been published.  

Cl2GaAsBu2 in Et20. Reaction of TolSb(SiMe3)2 (Tol = p-MeC H4) with Me3MCl (M= Ge or Sn) 

Me2NCH2-2-Ph2As-ferrocene (9), l-Me2NCH2-l, 2-(Ph2As)2-ferrocene and l-HOCH2-2-Ph2As- 

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J. L. Warden, Group V Arsenic, Antimony, and Bismuth, Organomet. Chem. 

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