A neutral, monomeric germanium(I) radical.

Stoichiometric reduction of the bulky β-diketiminato germanium(II) chloride complex [((But)Nacnac)GeCl] ((But)Nacnac = [{N(Dip)C(Bu(t))}(2)CH](-), Dip = C(6)H(3)Pr(i)(2)-2,6) with either sodium naphthalenide or the magnesium(I) dimer [{((Mes)Nacnac)Mg}(2)] ((Mes)Nacnac = [(MesNCMe)(2)CH](-), Mes = mesityl) afforded the radical complex [((But)Nacnac)Ge:](•) in moderate yields. X-ray crystallographic, EPR/ENDOR spectroscopic, computational, and reactivity studies revealed this to be the first authenticated monomeric, neutral germanium(I) radical.

Complexes of four-membered group 13 metal(I) N-heterocyclic carbene analogues with platinum(II) fragments.

A series of fluorinated bis(aryl)platinum(II) complexes, cis-[Pt(Ar(f))2(1,5-C6H10)] (Ar(f) = p-C6HF4, p-C6(OMe)F4 or C6H2F(3-)2,4,6) were reacted with the four-membered gallium(I) or indium(I) heterocycles, [:E{[N(Ar)]2CN(C6H11)2}] (E = Ga or In, Ar = C6H3Pr(i)(2-)2,6) under various stoichiometries. These yielded either the 2:1 complexes, cis-[Pt(Ar(f))2{Ga{[N(Ar)]2CN(C6H11)2}}2], trans-[Pt(C6H2F(3-)2,4,6)2{Ga{[N(Ar)]2CN(C6H11)2}}2] and trans-[Pt(Ar(f))2{In{[N(Ar)]2CN(C6H11)2}}2], or the 3:1 complexes, trans-[Pt(Ar(f))2{In{[N(Ar)]2CN(C6H11)2}}3] (Ar(f) = p-C6HF4 or p-C6(OMe)F4), all of which were crystallographically characterised. The differing outcomes of these reactions are explained in terms of the lesser nucleophilicity and greater electrophilicity of the indium heterocycle relative to its gallium counterpart.

A heterobimetallic gallyl complex containing an unsupported Ga-Y bond.

The synthesis and characterization of the first unsupported Ga-Y bond in [Y{Ga(NArCH)(2)}{C(PPh(2)NSiMe(3))(2)}(THF)(2)] (Ar = 2,6-diisopropylphenyl) is described; structural and computational analyses are consistent with a highly polarized covalent Ga-Y bond.

Gallyl lanthanide complexes containing unsupported Ln-Ga (Ln = Sm, Eu, Yb or Tm) bonds.

A series of bis(gallyl) lanthanide(ii) complexes, [Ln(II){Ga[(ArNCH)(2)]}(2)(tmeda)(2)] (Ln = Sm, Eu or Yb; Ar = C(6)H(3)Pr(i)(2)-2,6), and a gallyl thulium(iii) compound, [Tm(III){Ga[(ArNCH)(2)]}{(ArNCH)(2)}(tmeda)], have been prepared; the first structural studies of Ga-Tm and Ga-Sm bonded complexes are described.