Synthese und Koordinationschemie hemilabiler P,N‐Hybridliganden mit terminalen 2‐Pyridyl‐Donorgruppierungen
1994; Wiley; Volume: 127; Issue: 3 Linguagem: Inglês
10.1002/cber.19941270306
ISSN0009-2940
AutoresAntonella Heßler, Jörg Fischer, Stefan Kucken, Othmar Stelzer,
Tópico(s)Synthesis and characterization of novel inorganic/organometallic compounds
ResumoSynthesis and Coordination Chemistry of Hemilabile P,N‐Hybride Ligands with Terminal 2‐Pyridyl Donor Groups* 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 [2‐Py‐(CH 2 ) 2 ‐PR′H (R′ = H, Ph), HMeP‐(CH 2 ) 3 ‐PMeH] or by alkylation of organolithium phosphides, R 2 P‐(CH 2 ) 3 ‐PMeLi or 2‐Py‐(CH 2 ) 2 ‐PR′Li (R = Ph, i Pr; R′ = H, Ph), with 2‐(2‐chloroethyl)pyridine or di‐ tert ‐butylphosphetanium bromide. Upon reaction with NiBr 2 3 H 2 O or K 2 MCl 4 (M = Pd, Pt) the phosphanes (L) of type 2‐Py‐(CH 2 ) 2 ‐P(R′)‐(CH 2 ) m ‐PR 2 ( 1, 3, 6 ) form square planar Ni(II), Pd(II), and Pt(II) complexes of composition MX 2 (L) (10–14) . With NiBr 2 and K 2 MX 4 the tripod type phosphane 2 forms square pyramidal complexes [MX(2)]X (M = Ni, Pd; X = Cl, Br; 15, 16 ). An X‐ray structural analysis of [NiBr( 2 )] + Br − ( 15 ) reveals a distorted square pyramidal coordination geometry at Ni(II), the 2‐Py donor being in apical position with a long NiN bond [2.270(15) Å]. The tetradentate ligand 7 forms Ni(II), Pd(II), and Pt(II) complexes MX 2 ( 7 ) which for M = Pd, Pt show dynamic behaviour by exchange of the terminal Py donor groups. With [RhCl(COD)] 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 RhN distance [2.145(3) Å].
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