Coordination complexes of gallium(in) and indium(III) halides. III. Complexes of gallium(III) halides with 2,2′-bipyridyl

Abstract

The new complexes GaCl,(bipy), GaBr,(bipy),MeCN, GaBr,(bipy),, Ga13(bipy), and the related compounds [GaC12(bipy),]BF4, [GaCl,(b/py)

Preparation, Characterization, and Structural Systematics of Diphosphane and Diarsane Complexes of Gallium(III) Halides

“…The small chelate bite of the diphosphane results in quite acute ∠P−Ga−P of ∼82°. Six-coordination is also present in the 2,2‘-bipyridyl complexes [GaX 2 (2,2‘-bipy) 2 ][GaX 4 ], but the cations are cis isomers. , The diphosphane complexes are poorly soluble in chlorocarbons but give single sharp 31 P{ 1 H} NMR resonances with small high-frequency coordination shifts, showing them to be exclusively the trans isomers in solution. Only the [GaX 4 ] - anions were observed in the 71 Ga NMR spectra; fast relaxation in the lower-symmetry cations accounts for the absence of the resonances (see below).…”

Solid-state structures of group IIIb metal chloride adducts with 2,2',2''-terpyridyl

“…Considerable progress has been made in recent years toward an understanding of the solid-state structures of group Illb metal halide adducts with neutral nitrogen donors.1 Structural information has, for the most part, been obtained from far-infrared and Raman studies on crystalline solids.2-8 Single-crystal X-Ray structural determinations have established the detailed molecular stereochemistry in [GaCl2(bipy)2] [GaCh] (bipy = 2,2'bipyridyl)6 and GaCl3(terpy) (terpy = 2,2' ,2"terpyridyl).10 Vibrational spectroscopy has been most useful in the identification of tetrahalometalate ions MXr (M = Ga, In, Tl; X = Cl, Br, I) in the crystal lattices of complexes having ionic dimer structures. [4][5][6] In other cases however an unambiguous structural assignment may not be possible from solid-state infrared and Raman data. The complexes MC18(terpy) ( = Ga, In, Tl) appeared to be representative of the latter situation since limited spectroscopic studies on TICI3-(terpy)4 and GaCh (terpy)10 did not suffice to distinguish the trans octahedral structure I from the alternative ionic formulation II in which the cation (M = Ga, In) I I is isoelectronic (and presumably isostructural) with the trigonal-bipyramidal compounds MCl2(terpy) ( = Zn, Cd).…”