Reactivity of R₂AlH (R = Me, Buⁱ) with Selected Aminoarsines and Secondary Amines

Abstract

Me2AlH and Bui 2AlH were reacted with a series of nine aminoarsines, Me2AsR (R = NMe2, NPrn 2, NPri 2, NBun 2, NBui 2, NC4H8, NC5H10, NC6H12, and N(C2H4)2NMe), in C6D6 at room temperature, and the reactions were monitored by 1H and 13C NMR spectroscopy. The relative rates for initial As−N bond cleavage and final product formation were dependent on the steric requirements of the alkyl groups attached to aluminum and nitrogen in the starting materials. Overall rates were slower with Bui 2AlH than with Me2AlH for a given aminoarsine. For most of the reactions, the predominant Al-containing products were the dimeric aminoalane compounds, [Me2AlR]2 and [Bui 2AlR]2. Although Al−N bond formation was the prefered mode of reaction, Al−As bond formation was also observed when the bulky Pri and Bui aminoarsine derivatives were used. The [Bui 2AlR]2 compounds were synthesized independently by the reaction of Bui 2AlH and the respective amine or, in the case of [Bui 2AlNBui 2]2, by the reaction of Bui 2AlCl and LiNBui 2. X-ray crystal structures were determined for the compounds [Me2AlNC6H12]2, [Me2AlN(C2H4)2NMe]2, [Bui 2AlNMe2]2, and [Bui 2AlN(C2H4)2NMe]2. All of the compounds have planar Al2N2 rings with the exception of [Bui 2AlN(C2H4)2NMe]2, which displays a puckered Al2N2 ring.

Anthracene as a Launchpad for a Phosphinidene Sulfide and for Generation of a Phosphorus–Sulfur Material Having the Composition P2S, a Vulcanized Red Phosphorus That Is Yellow

“…Though successful for other strained chlorophosphines, we found reduction of ClP A with LiAlH 4 and similar nucleophilic hydride sources to give only decomposition, likely due to the fragility of the strained C–P–C bridge toward nucleophilic opening as in aziridines and phosphiranes. , Instead, treatment of Me 2 NP A with an electrophilic hydride source, di- iso -butylaluminum hydride (DIBAL-H, 2.2 equiv), in thawing toluene provided 5 ( 31 P δ 162 ppm, 1 J PH = 161 Hz) in fair yield (50%, Scheme ). A single-crystal X-ray diffraction study revealed structural parameters in line with those reported for other RP A species (Figure a). This light-sensitive compound was not found to fragment thermally into anthracene and phosphinidene HP̈: upon heating, in agreement with our current understanding of requisite substituent patterns for phosphinidene generation. , …”

Azepanium ionic liquids

“…Consistent with the discussion above for 1 H resonances, an anion effect is also observed on 13 C chemical shifts for carbon atoms one or two bonds away from the positively charged nitrogen atom in the azepanium ring. Furthermore, resonances for carbon atoms in the anions ([CF 3 CO 2 ] -, [OTf]and [NTf 2 ] -) are observed as quartets, as expected from the coupling to three 19 F nuclei.…”

“…Although azepane has been used as a ligand for both main group (e.g. aluminium) 19 and transition metal (e.g. platinum) 20 elements, there have been no studies in which it has been used as the basis for forming ionic liquids.…”

C−H Activation by AlCl Monomers: Characterization of HAl(Cl)CH3 as the Product of the Photoactivated Reaction Between AlCl and CH4 in a Solid Ar Matrix at 12 K

“…[24] In (Me 2-AlNC 6 H 12 ) 2 , an example for Al with a coordination number of 4, AlϪC bond lengths of 196.3(4) and 198.0(6) pm are adopted according to an X-ray diffraction analysis. [25] One further example is the compound [(tmpCO 2 ) 2 AlMe] 2 , which features an Al atom with a coordination number of 5 and an AlϪC distance of 195.2(4) pm. [26] In general, the AlϪC bond lengths cover a large range (189.7 to 236.6 pm) with an average of 198.3 pm according to the Cambridge Structural Database.…”