37943-90-1Relevant articles and documents
Synthesis and Characterization of a N,C,N-Carbodiphosphorane Pincer Ligand and Its Complexes
Klein, Marius,Xie, Xiulan,Burghaus, Olaf,Sundermeyer, J?rg
, p. 3768 - 3777 (2019)
The reaction of 2-pyridiyldiphenylphosphine (2) with tetrachloromethane and subsequent dehalogenation of the intermediate chloro phosphonium salt [(CDPPy2)Cl]Cl (3) with tris(1-pyrrolidyl)phosphine results in the formation of a new type of carbodiphosphorane N,C,N pincer ligand, sym-bis(2-pyridyl)tetraphenylcarbodiphosphorane, CDPPy2 (1). It crystallizes in a triclinic crystal system with a crystallographic point group of P1. This neutral double-ylidic N,C,N ligand is capable of stabilizing a wide range of metal coordination polyhedra, varying from square planar [(CDPPy2)PdCl]Cl (4), octahedral mer-[(CDPPy2)TiCl3] (5) and fac-[(CDPPy2)Cr(CO)3] (6) to trigonal-bipyramidal [(CDPPy2)MnCl2] (9) and [(CDPPy2)CoCl2] (10) complexes. Unprecedented dinuclear complexes are formed with molybdenum and nickel carbonyls. 1 reacts with [Mo(CO)3(NCMe)3] to form the symmetric κ3-N,C,N-[(CDPPy2)Mo(CO)3(μ-CO)Mo(CO)3] (7) with one bridging carbonyl next to a bridging central carbon atom with its two lone pairs. In contrast, an unsymmetrical coordination mode with only one coordinated pyridine is observed in κ2-N,C-[(CDPPy2)Ni(CO)(μ-CO)Ni(CO)2] (8). Carbodiphosphorane-based ligands are unique due to their σ,πfour-electron-donor character of the central carbon atom toward one metal and alternatively their 2σ four-electron-donor character toward two vicinal metal atoms.
The Trityl-Cation Mediated Phosphine Oxides Reduction
Landais, Yannick,Laye, Claire,Lusseau, Jonathan,Robert, Frédéric
supporting information, p. 3035 - 3043 (2021/05/10)
Reduction of phosphine oxides into the corresponding phosphines using PhSiH3 as a reducing agent and Ph3C+[B(C6F5)4]? as an initiator is described. The process is highly efficient, reducing a broad range of secondary and tertiary alkyl and arylphosphines, bearing various functional groups in generally good yields. The reaction is believed to proceed through the generation of a silyl cation, which reaction with the phosphine oxide provides a phosphonium salt, further reduced by the silane to afford the desired phosphine along with siloxanes. (Figure presented.).
Efficient potassium hydroxide promoted P-arylation of aryl halides with diphenylphosphine
Chen, Jin,Dai, Bencai,Liu, Changchun,Shen, Zhihao,Zhou, Yang
, (2021/06/26)
A simple synthetic method of triarylphosphine compounds by KOH-promoted P-Arylation reaction of aryl halides with diphenylphosphine is presented. Notably, this transformation could smoothly proceed with high yields under transition-metal-free and mild reaction conditions. In addition, this protocol is valuable for industrial application due to the convenient operation and readily accessible aromatic halides. A possible explanation of the reaction mechanism was proposed based on the experimental data.
