194655-62-4Relevant articles and documents
Synthesis of acyclic NPNCN systems and metalation reactions with organolithium, -magnesium, and -aluminum reagents
Chivers, Tristram,Copsey, May C.,Fedorchuk, Chantall,Parvez, Masood,Stubbs, Michael
, p. 1919 - 1928 (2005)
The preparation of a new family of acyclic DippN(H)P(Ph)NRCR′NR systems (2a-c) has been achieved by the reaction of the mono(amino) chlorophosphine PhP(Cl)N(H)Dipp (1; Dipp = 2,6-(iPr) 2C6H3) with 1 equiv of Li[CR′(NR) 2] (2a, R = tBu, R′ = nBu; 2b, R = Cy, R′ = tBu; 2c, R = Cy, R′ = nBu). Metalation reactions of 2a-c using nBuLi, Me3Al, and Bu2Mg have shown that the NPNCN backbone is susceptible to nucleophilic attack. Reactions of 2a or 2b with nBuLi or Me3Al, respectively, produce the complexes Li[DippNPhP-P(nBu)PhNDipp]· Et 2 (3) and Al(Me)2[DippNPhP-P(Me)PhNDipp] (4). These complexes involve a new type of N,N′ bidentate ligand with a chiral phosphorus center bearing bulky organic substituents on the nitrogen atoms. Reaction of 2c with Bu2Mg proceeds in a different manner, producing the amidinate complex Mg[CyNC(nBu)NCy][DippNP(nBu)Ph] ·Et2O (5). A more direct route to 3 and the analogous methyl-substituted complex Li[DippNPhP-P(Me)PhNDipp]·Et2)O (6), involving the reaction of 1 with the appropriate organolithium reagent in the molar ratio 2:3, has been developed. The oxidation product of 3, {Li[DippNPhP(O)P(nBu)PhNDipp]}2 (7), has also been synthesized via an alternative route. Complexes 1, 2a,b, and 5-7 were fully characterized by multinuclear NMR spectroscopy, elemental analysis, and X-ray crystallography.
Synthesis and structures of mono- and Bis(amidinate) complexes of aluminum
Coles, Martyn P.,Swenson, Dale C.,Jordan, Richard F.,Young Jr., Victor G.
, p. 5183 - 5194 (2008/10/08)
The synthesis and structures of mono- and bis(amidinate) aluminum complexes are described. The reaction of AlMe3 and 1 equiv of carbodiimide, R′N=C=NR′, affords {MeC(NR′)2}AlMe2 (1a, R′ = iPr; 1b, R′ = Cy = cyclohexyl). The reaction of R′N=C=NR′ with MeLi or tBuLi generates Li[RC(NR′)2] (2a, R = Me, R′ = iPr; 3a, R = tBu, R′ = iPr; 3b, R = tBu, R′ = Cy; 3c, R = tBu, R′ = SiMe3). 2a, 3a, and 3b may be isolated or reacted in situ, while attempted isolation of 3c gave [Li(tBuCN){μ,-N(SiMe3)2}]2 (3d). The reaction of 1 equiv of AlCl3 with 2a or 3a-c affords {RC(NR′)2}AlCl2 (4a, R = Me; 5a-c, R = tBu), and the reaction of AlMe2Cl with 3a-c affords (tBuC(NR′)2}AlMe2 (6a-c). Alkylation of 5a,b with 2 equiv of PhCH2MgCl or Me3CCH2Li yields {tBuC(NR′)2}Al(CH2Ph)2 (7a,b) or (tBuC(NR′)2}Al(CH2CMe3) 2 (8a,b). The reaction of 0.5 equiv of AlCl3 with 2a or 3a,b yields {RC(NR′)2}2AlCl (9a, R = Me; 10a,b, R = tBu). Complexes 1b, 3d, 4a, 5a,b, 6b, 8b, 9a, and 10a,b have been characterized by X-ray crystallography. The crystallographic results establish that steric interactions between the R and R′ groups influence the R′-N-Al angle and, hence, the steric environment at aluminum.