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Relevant academic research and scientific papers

A decagallane(6) cluster Ga10[Si(CMe3) 3]6 with an unprecedented structure

The decagallane(6) Ga10R′6 [R′ = Si(CMe3)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 [Ga10R′6] - as well as that of Ga10R″6 [R″ = Si(SiMe3)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.

The Hexagallane [Ga6{SiMe(SiMe3)2} 6] and the closo-Hexagallanate [Ga6{Si(CMe 3)3}4 (CH2C6H 5)2]2- - The Transition to an Unusual precloso-Cluster

The closo hexagallanate [Ga6R4(CH2Ph) 2]2- (R = SitBu3) as well as the hexagallane Ga6R6 (R = SiMe(SiMe3) 2) with only six cluster electron pairs were isolated from reactions of GaI with the corresponding silanides. The structure of the latter is derived from an octahedron by a Jahn-Teller-distortion and is different from the capped trigonal bipyramidal one expected by the Wade-Mingos rules. Both compounds were characterized by X-ray crystallography. The bonding is discussed with simplified Ga6H6 and Ga 6H62- models via DFT methods.

Octagallane (tBu3Si)6Ga8 and its reduction to (tBu3Si)6Ga82- - On the existence of isomeric gallium clusters

Thermolysis of the trigallanyl radical R*4Ga3 in heptane at 60 °C leads to the dark blue octagallane R*6Ga8 (R* = supersilyl SitBu3), as well as the digallanyl radical R*3Ga2 and the tetrahedro-tetragallane R*4Ga4. In addition, supersilyl radicals R* are formed which stabilize themselves either by dimerization or by addition of hydrogen atoms. R*6Ga8 can be reduced in THF with NaC10H8 to the dark-red octagallanediide Na2Ga8R*6·2THF. According to an X-ray structure analysis of R*6Ga8 and R*6Ga82- one finds that the Ga atoms of four R*Ga moieties, together with two naked Ga atoms, occupy the corners of a distorted octahedron; the naked Ga atoms themselves are located, along with Ga atoms of two further R*Ga moieties, at the corners of a distorted square. The reduction of R*6Ga8 leads only to a negligible shortening of the Ga-Ga distances from 2.64 to 2.61 A (mean values) in R*6Ga82-. Both the octagallanes possess Ga8 frameworks previously unknown for group 13 clusters. They are isomeric to the recently described Ga8 framework of the octagallane Tsi6Ga8 [Tsi = trisyl C(SiMe3)3]. Hence, not only boron but also the heavier group 13 atoms form isomeric clusters.