lithium amide in liquidammonia. The transition metal phosphane complex (R2N)2(H2N)PNi(CO)3 (3) was prepared by reaction of 2a with tetracarbonylnickel. N-Complexation of 2a with trimethylalane affords the iminophosphorane-alane adduct (R2N)2HP=N(H)AlMe3 (4) by 1,2-H shift from the nitrogen to the phosphorus atom. The corresponding reaction with aluminium trichloride leads to the formation of the salt
The ‘one-pot’ syntheses of α,α′-diphosphino-substituted imines: a unique reaction of bulky bis(dialkylamino)chlorophosphines
作者:Antoine Baceiredo、Guy Bertrand、Philip W. Dyer、John Fawcett、Nina Griep-Raming、Olivier Guerret、Martin J. Hanton、David R. Russell、Anna-Maria Williamson
DOI:10.1039/b009867l
日期:——
The reaction between various bis(dialkylamino)chlorophosphines and N-isopropyl-substituted lithium amides afforded bis(α,α′-phosphino)imines in a ‘one-pot’ procedure. These compounds react with sulfur to generate intramolecularly hydrogen-bonded ylide derivatives. The molecular structure of (Pr2iN)2PCH2C(NBut)CH2P(NPri)2 has been determined by X-ray crystallography.
Reactivity of bulky aminophosphanes towards small molecules: Activation of dihydrogen and carbon dioxide by aminophosphane/borane frustrated Lewis pairs
atoms. According to DFT calculations, these compounds are highly nucleophilic, with nucleophilic centers located on the N and P atoms. Except for species containing a PPh2 moiety, the obtained aminophosphanes are air-stable and do not react with water. They form stable frustrated Lewis pairs with BPh3 or B(C6F5)3. Mono- and bisaminophosphanes in the presence of B(C6F5)3 activate dihydrogen and carbon
Formation of nitrilimines and diazo compounds from lithiated and stannyl diazo derivatives: scope and mechanism
作者:Regis Reau、Guilaine Veneziani、Guy Bertrand
DOI:10.1021/ja00041a025
日期:1992.7
ophosphane (8) leading to a mixture of nitrilimine 9 and diazo derivative 10, in a 21/4 ratio. The reaction of [bis-(diisopropylamino)thioxophosphoranyl](triethylstannyl)diazomethane (11) with bis(diisopropylamino)chloroborane (12) gives C-[bis(diisopropylamino)thioxophosphoranyl]-N-[bis(diisopropylamino)boryl]nitrilimine (13), in 60% yield
(Phosphino)(Aryl)Carbenes: Effect of Aryl Substituents on Their Stabilization Mode
作者:Emmanuelle Despagnet-Ayoub、Stéphane Solé、Heinz Gornitzka、Alexander B. Rozhenko、Wolfgang W. Schoeller、Didier Bourissou、Guy Bertrand
DOI:10.1021/ja0281986
日期:2003.1.1
(phosphino)(aryl)carbenes, 1b-d, 10a,b, and 14a,b, were prepared by photolysis of their diazo precursors. The influence of the steric and electronic properties of the aryl ring on the structure and stability of these carbenes was studied both experimentally and theoretically. Among the different stabilization modes investigated, those featuring an acceptor as well as a spectator arylsubstituent result