Isolable Phospha- and Arsaalumenes

Abstract

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, *).

Contrasting E−H Bond Activation Pathways of a Phosphanyl‐Phosphagallene

“…[ 15 , 16 ] This series of interesting compounds was expanded to include examples of Al=P and Al=As double bonds by Braunschweig and Hering‐Junghans, who were able to access such species by reaction of (AlCp*) 4 with the phospha‐Wittig reagents Dipp TerPnPMe 3 (Pn=P, As). [17] …”

Titanocene pnictinidene complexes

“…To date there are two potential arsa-Wittig reagents described in the literature, Tip TerAsPMe3, 33 and Dip TerAsPMe3 (4). 34 Using an equimolar mixture of 4 and 1 in C6D6 at room temperature revealed a new signal in the 31 P NMR spectrum at ( 31 P) = 16.7 ppm after 8 h at room temperature and after heating the mixture to 80 °C over a period of 16 h full conversion of both 1 and 4 to the titanocene arsinidene complex [Cp2(PMe3)Ti=As Dip Ter] (5) was detected (Scheme 3, bottom). respectively.…”

Titanocene Pnictinidene Complexes

“…To date there are two potential arsa-Wittig reagents described in the literature, Tip TerAsPMe3, 33 and Dip TerAsPMe3 (4). 34 Using an equimolar mixture of 4 and 1 in C6D6 at room temperature revealed a new signal in the 31 respectively. 26 We note that using sub-stoichiometric amounts of 1 in the reaction with 4 reproducibly gave rise to the formation of the diarsene ( Dip TerAs)2 (6) as a side product.…”