John D. Gorden

Use of a smaller counterion results in an ‘inverse sandwich’ diindium cation

Treatment of In(C 5 Me 5 ) with [(toluene)H[[B(C 6 F 5 ) 4 ] affords the salt [In(η 5 -C 5 Me 5 )In][B(C 6 F 5 ) 4 ]. X-ray analysis indicates that the cation possesses an inverse sandwich structure, one indium atom of which experiences a close contact with a meta -fluorine of a C 6 F 5 group of a [B(C 6 F 5 ) 4 ] − counterion. The other indium atom exhibits a weak η 6 -interaction with a C 6 F 5 group of a different [B(C 6 F 5 ) 4 ] − anion.

The unusual reaction of Ga(C5Me5)3 with a nucleophilic carbene

Abstract Treatment of Ga(C5Me5)3 with tetramethylimidazol-2-ylidene affords the carbene complex, Ga(C5Me5)2H·carbene (1). The structure of 1 was determined by X-ray crystallography. Possible mechanisms for the formation of 1 are discussed.

Synthesis and structure of (η5-C5Me5)Ga→Al(C6F5)3. The first example of a gallium – aluminium bond

The reaction of [(η5-C5Me5)Ga]6 with Al(C6F5)3 results in (η5-C5Me5)Ga→Al(C6F5)3 (1), the first compound with a gallium-aluminium donor-acceptor bond. The structure of 1 was determined by single-crystal X-ray diffraction.

Gallium–boron donor–acceptor bonds

Examples of compounds with gallium-boron donor-acceptor bonds, HC[MeC(2,6-pri2C6H3)N]2Ga-->B(C6F5)3 3 and (eta 5-C5Me5)Ga-->B(C6F5)3 4 have been prepared by treatment of the free gallanediyls with B(C6F5)3; the structures of both compounds were determined by X-ray crystallography.

Triple-decker main group cations

The syntheses of the first main group triple-decker cations are described, namely, [(η5-C5Me5)Sn(μ-η5- C5Me5)Sn(η5-C5Me5 )][Ga(C6F5)4] and [(η6-C7H8)In(μ-η5-C 5Me5)In(η6-C7H8 )][(C6F5)3BO(H)B(C6F 5)3], both of which have been characterized by X-ray crystallography; the former was prepared by the reaction of Sn(η5-C5Me5)2 with Ga(C6F5)3, while the latter was prepared by treatment of [In(η5-C5Me5)]6 with an equimolar mixture of B(C6F5)3 and H2O·B(C6F5)3.

The structure of the decamethylborocenium cation: the most tightly-squeezed metallocene?

X-Ray crystallographic analysis along with DFT calculations on the decamethylborocenium cation provide definitive structural and electronic information about this most tightly-squeezed main group metallocene—the first to adopt the elusive σ/π geometry in the solid state.

A valence isomer of a dialane

The compound (η5-C5Me5)Al→Al(C6F 5)3, which is the first valence isomer of a dialane, has been prepared by treatment of [Al(η5-C5Me5)]4 with Al(C6F5)3 and characterized by X-ray crystallography and NMR spectroscopy.

Novel supramolecular architectures in group 13 perfluoroaryl complexes. Synthesis and structures of [AlMe(C6F5)(μ-Me)]2 and GaMe(C6F5)2

Novel supramolecular architectures are observed in the solid state structures of [AlMe(C6F5)(mu-Me)]2 (1) and Ga(C6F5)2Me (2) via pi-pi stacking between C6F5 rings and intermolecular aryl-F-->Ga interactions, respectively.