The gallium(I) derivative [Ga({N(dipp)CMe}(2)CH)] (1; dipp = 2,6-diisopropylphenyl) undergoes facile oxidative addition reactions with various element-hydrogen bonds including N-H, P-H, O-H, Sn-H, and H-H bonds. This was demonstrated by its reaction with triphenyltin hydride, ethanol, water, diethylamine, diphenylphosphane, and dihydrogen. All products were characterized by means of single-crystal X-ray structure determination, NMR spectroscopy, IR spectroscopy, and mass spectrometry.

The amino substituted gallatetrahedranes described herein, Ga4(tmp)4 [tmp = 2,2,6,6‐(tetramethylpiperidino)] and Ga4[N(SiMe3)dipp]4 (dipp = 2,6‐diisopropylphenyl), are the first oligomeric gallium(I) amides to be reported. These compounds are formed in a facile manner from “GaI”. A new hexagallane with an unusual structure is also described. The clusters were characterized by NMR and UV/Vis spectroscopy, single‐crystal X‐ray crystallography, and DFT calculations.(© Wiley‐VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany, 2007)

Subvalent Gallium Triflates – Potentially Useful Starting Materials for Gallium Cluster CompoundsBy reaction of GaCp* with trifluormethanesulfonic acid in hexane a mixture of gallium trifluormethanesulfonates (triflates, OTf) is obtained. This mixture reacts readily with lithiumsilanides [Li(thf)3Si(SiMe3)2R] (R = Me, SiMe3) to afford the cluster compounds [Ga6{Si(SiMe3)Me}6], [Ga2{Si(SiMe3)3}4] and [Ga10{Si(SiMe3)3}6]. By crystallization from various solvents the gallium triflates [Ga(OTf)3(thf)3], [HGa(OTf)(thf)4]+ [Ga(OTf)4(thf)3]−, [Cp*GaGa(OTf)2]2 and [Ga(toluene)2]+ [Ga5(OTf)6(Cp*)2]− were isolated and characterized by single crystal X ray structure analysis.

By reaction of the gallium(I) derivative Ga(4)tmp(4) (tmp = 2,2,6,6-tetramethylpiperidino) with Cr(CO)(5)(cyclo-octene), Co(2)(CO)(8), and Ni(cyclooctadiene)(2), respectively, the Gatmp complexes [Cr(CO)(5)Gatmp], (CO)(3)Cr(mu(2)-Gatmp)(3)Cr(CO)(3), (CO)(3)Co(mu(2)-Gatmp)(2)Co(CO)(3), and (tmpGa)(2)Ni(mu(2)-Gatmp)(3)Ni(Gatmp)(2) were obtained. The latter are described as derivatives of the binuclear metal carbonyls Cr(2)(CO)(9), Co(2)(CO)(8), and Ni(2)(CO)(7), where some or all carbonyls are replaced by the amino gallylene group. All compounds are characterized by spectroscopy and crystal structure analysis. The change of the bonding situation from localized two-center gallium metal bonds in the chromium derivative to three-center bonds in the cobalt complex is discussed by means of density functional theory calculations.

The decagallane(6) Ga(10)R'(6) [R' = Si(CMe(3))(3)] adopts a quite unusual structure, which might be described as being derived from a pentagonal bipyramidal core, which is threefold capped. An alternative description is that of a conjuncto-cluster. The structure of the anionic cluster [Ga(10)R'(6)](-) as well as that of Ga(10)R''(6) [R'' = Si(SiMe(3))(3)] are described as being built of fused octahedra. Thus, this family of decagallanes is unique in showing structural isomers in the cluster core, giving hints to the pathways of formation of these clusters, too. The novel cluster compound is characterized by X-ray crystallography. Isomeric decagallanes(6) and structural changes on reduction are studied by DFT methods.