Ga—C Bonds

Compounds containing Ga—C Bonds.—The reaction of Ga(g) and PN(g) in the presence of solid graphite produces gallium monocyanide (detected mass-spectrometrically) 507 

spectrum of the product, with some assignments, has been given.508 

An electron-diffraction study of GaMe3 gave the following structural parameters 509 r(GaC) 1.967 0.002, r(CH) 1.082 0.003 A, Z GaCH 112.1 0.8°, and Z.CGaC 118.6°. The methyl groups are freely rotating at room temperature. 

Some thermochemical parameters have been listed for Ga trialkyls.510 The trialkylgallium-halogeno complexes (R3GaX) (R = Me or Et, X = F or R = Me, X = Br) and [(R3Ga)2X] (R and X as before) have been prepared, and their vibrational spectra reported.511 

Compounds containing Ga—C Bonds.—Okawara has reviewed the 1973 literature on organo-derivatives of Ga and In.  

studies on solutions of GaMes in benzene can be interpreted as showing that a -TT-complex is formed.  

A study of the kinetics of ligand exchange in the systems EtjGa-l-MeaGajNEta and Me. Ga + Mc3Ga,NEt3 suggests that the mechanism is primarily dissociative in character.  

Tri-t-butylgallium can be prepared in 50—60% yield by the reaction of Bu MgCl with GaBrj in ethereal solution. It is photosensitive, and reacts with GaXs to give Bu GaX (X = Cl, Br, etc.). I.r. bands due to v(GaC2) were reported at 543 and 512 cm .  

Reactions of Me3P=CH2 with MeaMCl (M = Ga, In, or Tl) form the new dimethylmetaldimethylphosphonium-bis(methylides), [Me2MCH2PMe2CH2] . Dimers (n = 2) may be isolated, and these possess eight-membered ring structures (76). This structure stabilizes the inherently labile thallium(iii) derivative.  

---

GaCMe(CMe)2CMe but no significant shortening of the ring Ga—C bonds was observed. Nonetheless the, 3C NMR spectrum of the gallatabenzene... 

A mixed indium hydride halide complex, (l) InH2Cl (29) has been prepared from the 1 1 reaction of [InH2Cl(NMe3) ] with carbene (1) (R = Mes, R = H), as shown in Scheme iP The structure of (29) is monomeric with the geometry at the In center close to tetrahedral. The In-C distance (2.244(6) A) is similar to those observed in (28) (2.200(7) A) and (25) (2.253(5) A). A related mixed gallium hydride iodide complex (1) GaH2l (30) has been isolated from the reaction of (26) with GaT, with concomitant deposition of galhum metal. Complex (30) is isostructural with the related indium complex (29) and has a Ga-C bond distance of 2.022(4) A. 

Epitaxial films of GaN can be prepared with (Me2N)2GaN3]2, a molecule in which the Ga—C bonds have also been excluded ... 

The tri-azide [Ga(N3)3]oo is an ideal carbon-free (no N—C or Ga—C bonds) precursor to GaN . In its native form it can explode under the appropriate conditions. However, it is remarkably stable when complexed to Lewis bases. Although these compounds do not sublime, they can be used to form GaN in condensed phases ... 

Alkyl bromides react by oxidative addition with so-called Ga dibromide. With methyl or ethyl bromide isolatable compounds with one Ga—C bond are produced ... 

---