Triorganyl‐ and Diorganyloxozirconium Hydridoborates – Synthesis and Structures

Abstract

The reactions of Zr(OBu)4 and Zr(OEt)4 with H3B·THF in THF led to HB(OR)2 and B(OR)3, but no zirconium tetrahydroborate [(RO)4–nZr(BH4)n] could be isolated. On the contrary, the reactions of [tBu3CO]4–nZrCln and [tBu3SiO]4–nZrCln with LiBH4 generated the tetrahydroborates [(RO)3Zr(BH4)] and [(RO)2Zr(BH4)2]. These can be used to produce by hydroborate exchange dihydridodiorganyl borates [(RO)4–nZr(H2BC8H14)n] and byproducts. The structures of the new zirconium hydridoborates have been determined by X‐ray crystallography. Compound [(tBu3CO)3Zr(H2BC8H14)] shows site‐disordered dihydroborate units with agostic Zr–H–C interactions, while [(tBu3SiO)2Zr(H2BC8H14)2] is quite symmetric (C2/c). The corresponding tetrahydridoborates possess in most cases μ31‐bonded ZrH3BH groups.

Boron, aluminium, gallium, indium and thallium

“…305 Quantum chemical calculations have been used to investigate the potential of low valent indium hydride complexes, supported by N-heterocyclic carbene ligands, as potential hydrogen storage systems. 306 A novel series of InÁ Á ÁIn bond containing donor-acceptor complexes of the form [X( [18]crown-6)InÁ Á ÁInX 3 ] (X = OTf, Cl, Br or I) , which represent a new isomeric form of indium(II) halides, have been formed by using the univalent indium reagent [In( [18]crown-6)][OTf] as a donor and has been investigated by its reactions with acceptors including InX 3 (X = Cl, Br, I). 307 Reaction of the indium triphosphine complex ([o-i Pr 2 P(C 6 H 4 )] 3 In) with [Pd(P t Bu 3 ) 2 ] and [AuCl(SMe 2 )] have been shown to result in the formation of complexes with significant, but markedly different MÁ Á ÁIn (M = Pd or Au) interactions in the solid state.…”