Oxidative Addition, Reduction and Reductive Coupling: The Versatile Reactivity of Subvalent Gallium Cations.

Intrigued by the successful oxidative addition of a P-H bond to univalent Ga[Al(ORF)4] giving the unprecedented dicationic gallium hydride complex [H-Ga(PPh3)3][Al(ORF)4]2 (ORF = OC(CF3)3), the oxidative addition of E-Cl containing...

Electrocatalytic hydrogen evolution with gallium hydride and ligand-centered reduction

GaIII porphyrin is active for electrocatalytic hydrogen evolution with unusual features, including ligand-centered electron transfer and formation of post-transition metal hydride.

Theoretical investigation on spin-forbidden cooling transitions of gallium hydride

The feasibility of laser cooling of gallium hydride is investigated using ab initio quantum chemistry.

Magnesium, zinc, aluminium and gallium hydride complexes of the transition metals

Here we survey and organise the state-of-the-art understanding of the TM–H–M linkage (M = Mg, Zn, Al, Ga). We discuss the structure and bonding in these complexes, their known reactivity, and their largely unrealised potential in catalysis.

Hydrometallation of amino-dialkynylgermanes – a gallium hydride oligomer and intramolecular Lewis acid-base interactions

The compound H5C6(H)Ge[C(GaCMe3)=C(H)CMe3]2(μ-H)3[Ga(CMe3)2], 2, was isolated in trace quantities from the reaction of Et2N–Ge(C≡C–CMe3)3 with excess H–Ga(CMe3)2. Compound 2 has a unique molecular structure with a Ga3H3 heterocycle of which one Ga–H–Ga group is bridged by a dialkenylgermanium unit. The molecular structure of a second compound (3) is reported, which may be described as a spiro-germane and has AlNGeC and AlC2Ge heterocycles. The rings are formed by intramolecular Al–N and Al–C interactions.

Gallium hydride and monovalent indium compounds that feature tris(pyrazolyl)hydroborate ligands

The tris(pyrazolyl)hydroborate compounds [tris(3,5-dimethyl-1H-pyrazol-1-yl-κN2)hydroborato]indium(I), [In(C15H22BN6)], abbreviated as [TpMe2]In, and [tris(3-tert-butyl-5-methyl-1H-pyrazol-1-yl-κN2)hydroborato]indium(I), [In(C24H40BN6)], abbreviated as [TpBut,Me]In, represent well defined examples of three-coordinate monovalent indium. In both compounds, the geometry at indium is pyramidal and natural bond orbital (NBO) calculations indicate that the indium lone pair occupies an orbital that is primarily 5sin character. The trivalent gallium hydride compound hydrido[tris(3-tert-butyl-5-methyl-1H-pyrazol-1-yl-κN2)hydroborato]gallium(III) tetrachloridogallium(III), [Ga(C24H40BN6)H][GaCl4], abbreviated as {[TpBut,Me]GaH}[GaCl4], is obtainedviareaction of [TpBut,Me]Tl with [HGaCl2]2, and the Ga—H bond length of 1.49 (6) Å compares favorably with the mean value of 1.50 Å for structurally characterized gallium hydride compounds that are listed in the Cambridge Structural Database.