The
combination of (AlCp*)4, a source of monomeric :AlCp*
at elevated temperatures, with DipTerPnPMe3 (Pn
= P, As), so-called pnicta-Wittig reagents, at 80 °C cleanly
gives the pnictaalumenes DipTerPnAlCp* with polarized Pn–Al
double bonds and intramolecular stabilization through interactions
of Al with a flanking aryl group of the terphenyl substituent on Pn.
In contrast, using MesTerPPMe3, the reaction
with 2 equiv of :AlCp3t or :AlCp* afforded the three-membered
2π-aromatic ring systems MesTerP(AlCp
x
)2 (x = 3t, *).
No metal needed: Boron does the job! The activation of the inert dinitrogen molecule has fascinated chemists for ages. In a ground-breaking study Braunschweig and co-workers have now demonstrated that N activation can be achieved with the aid of the p-block element boron-a reactivity previously restricted to transition metals.
The reaction of lithium N-trimethylsilyl-amides of the type RN(SiMe3)Li with bismuth(iii) chloride yielded mono-, di- or triaminobismuthanes depending on the sterical demand of the anilide ligand R and the used stoichiometry. For the bulky Mes* substituent the reaction with BiCl3 resulted in the formation of a C-C coupling product as the main product besides a small amount of the expected Mes*N(SiMe3)BiCl2.
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