RESUMO
Bismuth(iii) TEMPOxide compounds have been synthesized from the coupling of Bi(ii) species with the TEMPOË radical. The steric profile of the supporting bis(amido)disiloxane ligand promotes different fluxional behaviour in solution, and DFT calculations suggest variation in the Bi-O bond character. These compounds are active catalysts for oxidative coupling of TEMPO and silane substrates, believed to proceed via metathesis of Bi-O and Si-H bonds followed by decomposition of bismuth-hydride intermediate species.
RESUMO
A rare terminal cadmium hydride complex [(BDI)CdH] (BDI = [{N(2,6-iPr2C6H3)C(Me)}2CH]) has been synthesised from [(BDI)CdCl] and LiEt3BH. The hydride can be reduced to the cadmium(i) dimer, [(BDI)CdCd(BDI)] upon treatment with a catalytic amount of diisopropyl- or dicyclohexylcarbodiimide.
RESUMO
Bis(amidodimethyl)disiloxane ligands derived from O{SiMe2N(H)R}2 (abbreviated as (NONR)H2) are a stable support for neutral and cationic bismuth compounds. Attempts to extend the series Bi(NONR)Cl (R = Ar = 2,6-iPr2C6H3; R = tBu) to include compounds where R = Ar' = 2,6-Me2C6H3 were complicated by concomitant formation of the bimetallic compound {Bi(NONAr')}2(µ-NONAr'). Compounds containing [Bi(NONR)]+ cations were obtained from reactions with group 13 chlorides MCl3 (M = Al, Ga). X-ray crystallographic analysis showed intermolecular interactions with the [MnCl(3n+1)] anion.
RESUMO
Phenyl isocyanate inserts into the Bi-P bond of the terminal phosphanide Bi(NONAr)(PCy2) (NONAr = [O(SiMe2NAr)2]2- Ar = 2,6-iPr2C6H3) to afford the κ2N,O-phosphanylcarboxamidate complex. Liberation of the hydrophosphination product from the metal is achieved by reaction with HPPh2. The diphenylphosphanide product, Bi(NONAr)(PPh2), is however unstable and decomposes to generate reduced species, preventing catalytic turnover.
