COORDINATION COMPLEXES CONTAINING MULTI DENTATE LIGANDS. PART IV. REARRANGEMENT REACTIONS OF LOW SPIN PENTACOORDINATE NICKEL (II) COMPLEXES WITH SODIUM TETRAPHENYLBORATE TO PRODUCE POLYNUCLEAR COMPLEX SPECIES

Publisher Website
Google Scholar
Abstract
The reaction of the terdentate arsine bis(3-dimethylarsinopropyl)phenylarsine, tasp, with nickel(II) halides produces the diamagnetic, square-pyramidal [Ni(tasp)X2] (X =Cl, Br, I) complexes. In contrast to bis(3-dimethylarsinopropyl)methylarsine, the tasp ligand does not form a simple [Ni(ligand)(NCS)2] complex, but forms [Ni2 (tasp)(NCS)4], which can be subsequently converted to [Ni2(tasp)3(NCS)4]. Reaction of [Ni2(tasp)3(H2O)](ClO4)4 with varying amounts of sodium tetraphenylborate produces the polynuclear species [Ni2(tasp)3(H2O)](ClO4)(BPh4)3, [Ni3(tasp)5](C1O4)5(BPh4), and [Ni(tasp)2](BPh4)2. Similar reactions with [Ni(tasp)I2 produce the polynuclear [Ni2(tasp)2I3]BPh4, [Ni4(tasp)4I7]BPh4, and Ni2(tasp)3I4 species. All these polynuclear complexes are pentacoordinate and essentially square-pyramidal. The complexes were characterised by elemental analyses, magnetic, and visible and infrared spectral measurements, and by conductivity studies. The spectra and structures of the complexes are discussed.