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Issue 2, 1998
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New mono- and di-nuclear complexes of PdII, PtII and NiII of PNNP ligands with a 2,2′-biaryl bridging unit

Abstract

The Schiff bases 2,2′-bis{N-[(2-diphenylphosphino)phenyl]formimidoyl}biphenyl (L1) and 2,2′-bis{[(2-diphenylphosphino)benzylidene]amino}biphenyl (L2) were synthesized from the appropriate amine and aldehyde. Their co-ordination behaviour towards PdII, PtII and NiII has been studied. Dinuclear complexes were formed when treating L1 with 2 equivalents of [PdCl(Me)(cod)] (cod = cycloocta-1,5-diene) and Pd(O2CMe)2. In the case of the reaction of L1 with Pd(O2CMe)2 an unexpected double cyclopalladated complex was formed. However, treatment of L1 with 2 equivalents of [PtCl2(MeCN)2] resulted in hydrolysis of the ligand and a mononuclear complex of (2-diphenylphosphino)benzenamine was obtained. The structure of [Pd2L1Cl2Me2] 1 has been established by an X-ray diffraction study. The dihedral angle between the biphenyl rings is 49.2(8)° and the intramolecular Pd  · · ·  Pd distance is 7.165(3) Å. The biphenyl bridging moiety shows a remarkable bending of 169.2(8)°. Treatment of 1 with carbon monoxide resulted in a double CO insertion, yielding the bis(acetyl)palladium compound [Pd2L1Cl2{C(O)Me}2] 2. The structure of [Pd2L1(O2CMe)2]·4CH2Cl2 3 was also determined by X-ray diffraction. The dihedral angle between the biphenyl rings is 75.9(14)° while the intramolecular Pd  · · ·  Pd distance is 8.655(2) Å. The reaction of L2 with 2 equivalents of anhydrous [PdCl2(MeCN)2] or NiCl2 afforded mononuclear complexes. The crystal and molecular structure of [PdL2]Cl2·3.5CH2Cl2 was determined. The compound has an approximately square-planar P2N2 geometry.

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Supplementary files


Article type: Paper
DOI: 10.1039/A704170E
Citation: J. Chem. Soc., Dalton Trans., 1998,0, 263-270

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    New mono- and di-nuclear complexes of PdII, PtII and NiII of PNNP ligands with a 2,2′-biaryl bridging unit

    A. G. J. Ligtenbarg, E. K. van den Beuken, A. Meetsma, N. Veldman, W. J. J. Smeets, A. L. Spek and B. L. Feringa, J. Chem. Soc., Dalton Trans., 1998, 0, 263
    DOI: 10.1039/A704170E

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