Search

Solid Ba(OH)2 suspended in toluene containing HMPA [OP(NMe2)3] reacts with the 5-aminothiatriazole, naphthyl NH·[graphic omitted], to give the monomeric 5-mercaptotetrazolylbarium complex, [naphthlyl [graphic omitted]a·3HMPA, 1; the isolation and structural characterisation of 1 sheds new light on the known alkali-promoted rearrangement of 5-amino-substituted thiatriazoles into 5-thio-substituted tetrazoles.

The reaction of LiBu n with [(mes) 2 P(H)O] affords the diorganophosphinate complex [(mes) 2 P(O) 2 Li·2thf] 1 and [(mes) 2 PLi], however, addition of [Cd{N(SiMe 3 ) 2 } 2 ] to the mixture gives the diorganophosphinite complex [{Me 3 - Si) 2 N}Cd{(mes) 2 PO} 2 Li·2thf] 2; the formation of these complexes illustrates that the ligand functionality of 1 can be controlled by the character of the coordinated metal ion.

Dilithio-1,2,3-triphenylguanidide, [{(PhN)3C}Li2], reacts with [Cd{N(SiMe3)2}] to give [{(Me3Si)2N}2Cd{(PhN)3}Li2·3thf] 1; a novel co-complex containing three different metal coordination environments.

Nucleophilic substitution of the bis(trimethylsilyl)amido groups of [M{N(SiMe3)2}2](M = Zn or Cd) and [In{N(SiMe3)2}3] was found to be a halide-free and homogeneous approach to organometallic and metalloorganic complexes. The breadth of this new synthetic approach is illustrated by the formation of [Cd(SCPh3)2(tmen)]1(tmen = Me2NCH2CH2NMe2), [(PhC≡C)4Zn{Li(tmen)}2]2 and [Li(thf)4][In(C≡CPh)4]3(thf = tetrahydrofuran) from nucleophilic substitution reactions utilising [M{N(SiMe3)2}2](M = Zn or Cd) and [In{N(SiMe3)2}3], the outcome of which is dependent upon the Lewis bases and nucleophiles employed and the metal centres concerned. The crystal structures of complexes 1–3 have been determined.