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Stabilization of a two-coordinate, acyclic diaminosilylene (ADASi): completion of the series of isolable diaminotetrylenes, :E(NR(2))(2) (E = group 14 element).
An extremely bulky boryl-amide ligand has been utilised in the preparation of the first isolable, two-coordinate acyclic diaminosilylene (ADASi), shown to have a frontier orbital energy separation, and presumed level of reactivity, intermediate between those of the two classes of previously reported isolable two- coordinate, acYclic silylenes. Expand
A Systematic Study of Structure and E-H Bond Activation Chemistry by Sterically Encumbered Germylene Complexes.
The results of these reactivity studies imply that the use of the very strongly σ-donating boryl or silyl substituents is an effective strategy for rendering metallylene complexes competent for E-H bond activation. Expand
Cooperative bond activation and catalytic reduction of carbon dioxide at a group 13 metal center.
The hydride complex derived from the activation of H2 is shown to be a competent catalyst for the highly selective reduction of CO2 to a methanol derivative and represents the first example of a reduction process of this type catalyzed by a molecular gallium complex. Expand
Stable GaX2, InX2 and TlX2 radicals.
The first thermally robust monomeric MX2 radicals of gallium, indium and thallium are reported, which reveal facile one-electron shuttling processes at the metal centre. Expand
Exploiting Electrostatics To Generate Unsaturation: Oxidative Ge=E Bond Formation Using a Non π-Donor Stabilized [R(L)Ge:](+) Cation.
The two-coordinate germanium cation [(IDipp){(Me3Si)2CH}Ge:](+) has been synthesized, which lacks π-donor stabilization of the metal center and consequently has a very small HOMO-LUMO gap (187 kJExpand
Expanded-ring N-heterocyclic carbenes for the stabilization of highly electrophilic gold(I) cations.
Complexs of the type (NHC)AuH have been synthesised and shown to feature significantly more electron-rich hydrides than those based on ancillary imidazolylidene donors, consistent with the stronger σ-donor character of these NHCs. Expand
Coordination and activation of Al-H and Ga-H bonds.
The modes of interaction of donor-stabilized Group 13 hydrides (E=Al, Ga) were investigated towards 14- and 16-electron transition-metal fragments and β-Diketiminato ('nacnac')-st stabilized systems, {HC(MeCNDipp)2 }EH2, show more diverse reactivity towards Group’6 carbonyl reagents. Expand
Formation of sub-valent carbenoid ligands by metal-mediated dehydrogenation chemistry: coordination and activation of H2Ga{(NDippCMe)2CH}
Reactions of the β-diketiminato (‘Nacnac’) stabilized gallium dihydride H2Ga{(NDippCMe)2CH} with a range of mono- and dinuclear metal carbonyl reagents are characterized by loss of dihydrogen andExpand
Cobalt Boryl Complexes: Enabling and Exploiting Migratory Insertion in Base-Metal-Mediated Borylation.
Alkene functionalization by boryl transfer, a well-known reaction for noble metals such as Rh or Pt, can thus be effected by an 18-electron base-metal complex. Expand
Circumventing redox chemistry: synthesis of transition metal boryl complexes from a boryl nucleophile by decarbonylation.
An archetypal organometallic mode of reactivity, carbonyl extrusion, has thus been shown to be applicable to the boryl ligand class, with (13)C isotopic labeling studies confirming a dissociation/migration pathway. Expand