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The ion-separated complex 2[Li(thf) 4 ] + [Mn(C 12 H 8 N) 4 ] 2- 1 has been obtained from the nucleophilic substitution reaction of [Mn{N(SiMe 3 ) 2 } 2 ]·2thf with Li[C 12 H 8 N] (1∶4 equivalents) (thf = tetrahydrofuran, C 12 H 8 N = carbazol-9-yl), and the molecular species [Mn(C 12 H 8 N) 2 ]·3thf 2 from the acid–base reaction of [Mn{N(SiMe 3 ) 2 } 2 ]·2thf and C 12 H 8 NH (1∶2 equivalents). They are among the few amidomanganese(II) complexes containing simple (sterically undemanding) dialkyl- or diaryl-amido groups to be characterised. The crystal structures of both were determined: 1 contains the first tetraamidomanganese(II) dianion and 2 possesses the highest co-ordination number for Mn II in such a compound.

Cp 2 Cd.TMEDA 1 and Cp 2 Cd.PMDETA 2 have been synthesized and characterized by spectroscopic studies and by X-ray diffraction studies at low-temperature (153 K). The adducts are present in the crystals as mononuclear complexes. When the denticity of the Lewis base ligands in these adducts is increased (from two in 1 to three in three in 2 ) the Cd 2+ centre requires less electron density from the Cp ligands and the hapticity changes from η 2 − in 1 to η 1 − in 2 . Complexes 1 and 2 are the first compounds for which π-bonding of Cp ligands to Cd 2+ has been observed in the solid state.

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.

The heterogeneous reaction of elemental selenium with the monomeric complex [Cd(CCPh)2(tmen)](2:1 equivalents) produced the unusual loosely linked dimer [{Cd(SeCCPh)2(tmen)}2].

Metallation of diphenylphosphine with ZnEt2(5:3 equiv. ) in thf produces {[EtZn(µ-PPh2)]3·(HPPh2)2·thf}1, which is shown by X-ray crystallography to have a Zn3P3 core in which Ph2PH ligands act as donors to two of the zinc centres.

The syntheses of the monomeric diorganocadmium complex [Cd(PhCC)2(tmeda)]1, the first structurally characterised Cd-acetylide, and of the ion-separated [Cd(C12H8N)4]2–·2Li(thf)4+2, containing a metallo-organic Cd dianion, from the nucleophilic substitution reactions of Cd(NSiMe3)2 with PhCCLi (1 : 1 or 1 : 2 equiv.) and with C12H18NLi (1 : 1–4 equiv.) respectively, exemplify a new, halide-free and general route to metallo-organic complexes.

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.