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Synthesis and Coordination Chemistry of Hemilabile P,N-Hybride Ligands with Terminal 2-Pyridyl Donor Groups
Hessler, Antonella,Fischer, Joerg,Kucken, Stefan,Stelzer, Othmar
, p. 481 - 488 (2007/10/02)
P,N-hybride ligands 1-7 containing terminal 2-pyridyl donor groups have been obtained by base-catalyzed addition of diphenylvinylphosphane or 2-vinylpyridine to primary or secondary phosphanes or by alkylation of organolithium phosphides, R2P-(CH2)3-PMeLi or 2-Py-(CH2)2-PR'Li (R = Ph, iPr; R' = H, Ph), with 2-(2-chloroethyl)pyridine or di-tert-butylphosphetanium bromide.Upon reaction with NiBr2*3H2O or K2MCl4 (M = Pd, Pt) the phosphanes (L) of type 2-Py-(CH2)2-P(R')-(CH2)m-PR2 (1, 3, 6) form square planar Ni(II), Pd(II), and Pt(II) complexes of composition MX2(L) (10-14).With NiBr2 and K2MX4 the tripod type phosphane 2 forms square pyramidal complexes X (M = Ni, Pd; X = Cl, Br; 15, 16).An X-ray structural analysis of (+)Br(-) (15) reveals a distorted square pyramidal coordination geometry at Ni(II), the 2-Py donor being in apical position with a long Ni-N bond .The tetradentate ligand 7 forms Ni(II), Pd(II), and Pt(II) complexes MX2(7) which for M = Pd, Pt show dynamic behaviour by exchange of the terminal Py donor groups.With 2 the tridentate ligands L (1 and 3) yield complexes of composition RhCl(L) (20, 21).The structure of 20 has been determinated by X-ray diffraction.The ligand 3, acting in a tridentate manner, is coordinated to Rh(I) in a distorted square-planar arrangement with a normal Rh-N distance . - Key Words: 2-Pyridylalkylphosphanes / Hemilabile ligands / Nickel complexes / Palladium complexes / Platinum complexes
