Copper(I) Complexes with Trispyrazolylmethane Ligands: Synthesis, Characterization, and Catalytic Activity in Cross-Coupling Reactions

被引:31
作者
Haldon, Estela [2 ]
Alvarez, Eleuterio [3 ]
Carmen Nicasio, M. [1 ]
Perez, Pedro J. [2 ]
机构
[1] Univ Seville, Dept Quim Inorgan, Seville 41071, Spain
[2] Univ Huelva, Ctr Invest Quim Sostenible CIQSO, Dept Quim & Ciencias Mat, Lab Catilisis Homogenea,Unidad Asociada CSIC, Huelva 21007, Spain
[3] Univ Seville, CSIC, Inst Invest Quim Isla Cartuja, Seville 41092, Spain
关键词
N BOND FORMATION; ARYL HALIDES; C-N; AMINO-ACID; STRUCTURAL-CHARACTERIZATION; NITROGEN-HETEROCYCLES; CRYSTAL-STRUCTURES; IODIDE COMPLEXES; DIAMINE LIGANDS; MILD CONDITIONS;
D O I
10.1021/ic300843a
中图分类号
O61 [无机化学];
学科分类号
070301 ; 081704 ;
摘要
Three novel Cu(I) complexes bearing tris(pyrazolyl)-methane ligands, Tpm(x), have been prepared from reactions of equimolar amounts of CuI and the ligands Tpm, (HC(pz)(3)), Tpm*, (HC(3,5-Me-2-pz)(3)), and Tpm(Ms), (HC(3-Ms-pz)(3)). X-ray diffraction studies have shown that the Tpm and Tpm(Ms) derivatives exhibit a 2:1 Cu:ligand ratio, whereas the Tpm* complex is a mononuclear species in nature. The latter has been employed as a precatalyst in the aryladon of amides and aromatic thiols with good activity. The synthesis of a Tpm*Cu(I)-phthalimidate, a feasible intermediate in this catalytic process, has also been performed. Low temperature H-1 NMR studies in CDCl3 have indicated that this complex exists in solution as a mixture of two, neutral and ionic forms. Conductivity measurements have reinforced this proposal, the ionic form predominating in a very polar solvent such as DMSO. The reaction of Tpm*Cu(I)-phthalimidate with iodobenzene afforded the expected C-N coupling product in 76% yield accounting for its role as an intermediate in this transformation.
引用
收藏
页码:8298 / 8306
页数:9
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