Chloride ligands solid-state synthesis

A few years later Arnold and co-workers also reported the synthesis of lithium complexes of the neutral and anionic salts of a tridentate amino bis-carbene ligand (Scheme 2).13 Treatment of the cationic amino bis-imida-zolium salt with three equivalents of //-butyl lithium affords the lithium amino bis-carbene chloride complex (5). Deprotonation with four equivalents of n-butyl lithium affords the lithium amide salt (6). Although the complexes were not characterised in the solid state, characteristic shifts in the multinuclear NMR spectra and elemental analysis are consistent with the lithium complexes being formed. NMR spectra of 5 suggest formation of a cluster of lithium chloride ions with lithium-NHC bonds (13C NMR NCN 203.9 ppm) and NH-chloride bonding interactions. Following further deprotonation to form 6 the complex also retains lithium chloride and exhibits a similar C2 chemical shift (13C NMR NCN 203.4 ppm). 

In our own laboratory, we have reported the synthesis of a new Rh/Ti heterobimetallic complex 75 by reacting the 1,2-titanocenyl diphosphane ligand 74, nicknamed TiPHOS, with [Rh(cod)2](OTf) (Scheme 43) [129, 130]. The strucmre of 75 was determined by X-ray diffraction smdy and dynamic NMR smdies. A weak bonding interaction between one of the two chloride atoms of the TiPHOS ligand and the Rh center has been observed both in solution and in the solid state. The catalytic activity of complex 75 has been tested for the hydrosilylation of aromatic and aliphatic... 

A new complex formed between endo-dicyclopentadiene and gold(I) chloride has been prepared by a substitution reaction in dichloromethane, whereby carbon monoxide in dissolved [AuCl(CO)] has been displaced by the endo-dicyclopentadiene ligand/-The first example of the use of the Hofmann/Fischer reagent cyclopentadienylindium(I) for carbon-carbon bond formation and the demonstration of a one-pot tandem addition/intramolecular Diels Alder reaction in aqueous media have been reported/ The synthesis and solid-state structures of two new beryllocenes have been reported. These are [Be(CsMe4H)2] and [Be(C5Mes)2], which are obtained in the metathesis reactions of the potassium salts of the cyclopentadienes with beryllium dichloride, the former at room temperature and the latter at elevated (115 °C) temperature. ... 

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