678172-40-2Relevant academic research and scientific papers
Amido phosphine complexes of zinc: Synthesis, structure, and catalytic ring-opening polymerization of ε-caprolactone
Liang, Lan-Chang,Lee, Wei-Ying,Tsai, Tzung-Ling,Hsu, Yu-Lin,Lee, Ting-Yu
, p. 8748 - 8758 (2011/01/08)
A series of diarylamido phosphine ligands of the type N-(2- dihydrocarbylphosphinophenyl)-2,6-dialkylanilide 1a-d have been prepared and employed to investigate the coordination chemistry of zinc. Protonolysis of ZnMe2 with one equivalent of N-(2-diphenylphosphinophenyl)-2,6- dimethylaniline (H[1a]) produced a mixture of [1a]ZnMe (2a) and Zn[1a] 2 (4a), whereas that involving ZnEt2 gave exclusively the three-coordinate [1a]ZnEt (3a). In contrast, treatment of ZnR2 (R = Me, Et) with N-(2-diphenylphosphinophenyl)-2,6-diisopropylaniline (H[1b]), N-(2-diisopropylphosphinophenyl)-2,6-dimethylaniline (H[1c]), or N-(2-diisopropylphosphinophenyl)-2,6-diisopropylaniline (H[1d]) under similar conditions generated quantitatively the corresponding three-coordinate zinc methyl 2b-d and zinc ethyl 3b-d. The bis-ligand complexes 4a,b,d were isolated by either protonolysis of alkyls 2-3 with one equivalent of H[1] or metathesis of ZnX2 (X = Cl, OAc) with the corresponding lithium derivatives 5. Attempts to prepare [1a-d]ZnX (X = Cl, OAc) were not successful regardless of stoichiometry of the starting materials employed. Alcoholysis of zinc alkyls 2-3 led undesirably to protonation on the amido nitrogen donor of 1, highlighting perhaps its higher basicity than alkyls. The reaction of ZnCl2 with H[1c] generated the phosphorus-bound adduct {H[1c]ZnCl(μ-Cl)}2 (6c). Interestingly, attempts to deprotonate 6c with n-BuLi produced unexpectedly the alkylated product [1c]Zn(n-Bu) (7c) instead of [1c]ZnCl; analogous reactions employing NEt3 led to Lewis base substitution to give H[1c] and [ZnCl2(NEt3)]2. Structural characterization of all new compounds was achieved by multi-nuclear NMR spectroscopy (1H, 13C, 31P, and 7Li) and X-ray crystallography (2c-d, 3c, 4d, 5c-d, and 6c) where appropriate. On the basis of the NMR and X-ray data, in combination with the synthetic investigations, the steric nature of these amido phosphine ligands is recognized to follow the order of 1a 1b 1c 1d. Interestingly, zinc alkyls 2-3 are all active initiators for catalytic ring-opening polymerization of ε-caprolactone whereas the bis-ligand complexes 4 are not.
Microwave-assisted synthesis of phenylene-bridged aminophosphine ligands: Acceleration of N-arylation and aryl fluoride phosphorylation reactions
Seipel, Kelsey R.,Platt, Zed H.,Nguyen, Minh,Holland, Andrew W.
, p. 4291 - 4294 (2008/09/20)
(Chemical Equation Presented) Hindered β-aminoarylphosphines show promise as bidentate ligands for metal centers, but their reported synthesis requires heating at high temperatures for several days. Herein are reported conditions by which the two steps composing this synthesis, Buchwald-Hartwig amination and nucleophilic phosphorylation reactions, may both be completed in less than 3 h using microwave irradiation. The effects of several parameters on the outcome of the amination reaction are discussed, as are some indications of the scope within which each of these microwave protocols is effective.
Ligands for metals as catalysts for carbon-carbon bond formation
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Page/Page column 18, (2008/06/13)
The present invention provides a family of novel and stable ligands which chelate with a metal to form a complex. The ligand contains a ring, particularly a phenyl group, or a hydrocarbon group which links an amino group and PR1R2, NR1R2, OR1, SR1, or AsR1R2 group such that the structure of the ligand can be stabilized.
Metal complexes for catalytic carbon-carbon bond formation
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Page/Page column 16-17, (2010/02/15)
The present invention relates to a complex comprising a novel and stable ligand and a metal center. The ligand contains a ring, particularly a phenyl group, or a hydrocarbon group which links an amino group and PR1R2, NR1R2, OR1, SR1, or AsR1R2 group such that the structure of the ligand can be stabilized.
Catalytic carbon-carbon bond formation
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, (2008/06/13)
The present invention mainly relates to a carbon-carbon bond formation catalyzed by a complex comprising a novel and stable ligand and a metal center. The ligand uses a ring, particularly a phenyl group, or a hydrocarbon group to link an amino group and PR1R2, NR1R2, OR1, SR1, or AsR1R2 group for stabling the structure of the ligand.
