COORDINATION COMPLEXES OF GROUP (IV) HALIDES: PREPARATION AND INFRARED SPECTRA OF COORDINATION COMPOUNDS OF TITANIUM TETRACHLORIDE, TITANIUM TETRABROMIDE, ZIRCONIUM TETRACHLORIDE, AND TIN TETRACHLORIDE WITH Α,ω-Dinitriles AS LIGANDS

Abstract

Coordination complexes between dinitriles of dicarboxylic acids and tetrahalides of titanium, zirconium, or tin have been prepared. The analytical results and the infrared spectra indicate that on working under different experimental conditions three types of compounds are obtained: 2MX4.L-L, MX4.L-L, and MX1.2L-L where M X 4 is a Lewis acid and L-L a bidentate ligand. The compounds 2MXd.L-L are explained by the formation of halogen bridging between the two metal atoms. The compounds MX4.L-L are considered to be either coordination polymers or chelates of variable ring size and the compounds MX4.2L-L, ordinary addition compounds where no chelation takes place because of the mutual interaction of the two CN groups in a dinitrile of a short chain length.

Reaction of Vanadyl Ions with Alkyl Dinitriles

“…Their bondings are analogous to those reported for [Pt(P(CcH5)3)2(NC -CHoCHo -CN) ] 20 and [M (CO) 3 (NC -CH2CH2 -CN The vanadyl complex of succinonitrile is much less susceptible to dissociation in DMF than its malononitrile counterpart. Their molar conductivities were found to be 14.9 and 40 ohm -1 cm -2 mole -1 , respectively.…”

“…Complexes of group (IV) halides with dinitriles N = C -(CHo) " -C = N have been studied 2 extensively while chelates with such dinitriles are neither of these metal ions [3][4] nor of copper (I) Perchlorate 5 . Jain and Rivest ^ 6 prepared complexes of aminonitriles R2N -(CH2) " -C = N with titanium, tin and zirconium tetrahalides and have shown from molecular weight and conductivity data that these complexes were monomeric, non-ionic compounds.…”

Coordination Complexes of Group (Iv) Halides: Preparation of the Complexes of Titanium Tetrachloride, Titanium Tetrabromide, and Tin Tetrachloride With Some Thio-, Isothio-, and Iso-Cyanate Ligands

“…The experimental setup and the method of preparation of the complexes were quite similar to the ones used previously (1,4). The Lewis acids used were purified by appropriate methods as mentioned in a previous publication (I).…”

Co-Ordination Complexes of Group (Iv) Halides: Preparation and Infrared Spectra of the Co-Ordination Compounds of Titanium Tetrachloride, Titanium Tetrabromide, Zirconium Tetrachloride, Tin Tetrachloride, and Boron Trichloride With Ethyl Cyanoacetate as Ligand

“…T h e solvent carbon tetrachloride was made anhydrous by appropriate method. The group (IV) halides were purified as mentioned in previous publication (1 The group (IV) halides and their colnpleses are estremcly sensitive to humidity. Therefore, all manipulations were carried out in a rigorously dried apparatus and handled in an anhydrous chamber, \\~hich was continuously flushed with dry nitrogen in a manner describeel in an earlier paper (4).…”