Advances in Inorganic Chemistry, Vol. 41 by A. G. Sykes

By A. G. Sykes

Advances in Inorganic Chemistry offers well timed and informative summaries of the present growth in quite a few topic parts inside of inorganic chemistry starting from bio-inorganic to sturdy country reviews. Thisacclaimed serial beneficial properties studies written by way of specialists within the region and is an essential connection with complex researchers. each one quantity of Advances in Inorganic Chemistry comprises an index, and every bankruptcy is absolutely referenced.

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These results indicate a low affinity of Tc(II1) for halide and the possibility of preparing [ T c ( O H ~ ) ~in] ~a+weakly coordinating aqueous medium (2311, The stability of the mixed-valence [ T C " ' ~ ' ' ~ C ~ ~ ] ~ and the apparent inability to prepare [ T c " ' ~ C ~ ~were I ~ - a puzzle for a number of years in view of the stability of [Re2C1,12- and the only fleeting existence of [RezC1813-(159). However, in 1980 the brightgreen (NBU,)~[TC~C~,] was prepared by the reduction of [TCCl6I2-with Zn/HC1 and converted to the carmine-red ( N B U ~ ) ~ [ T C ,by B ~ligand ~I by exchange with HBr (232).

7 BM, consistent with a d3 configuration (379). The reaction of [TcOCl,]- with aromatic amines and dppe in refluxing alcohols gives the purple air-stable imido complexes [TcCl(NAr)(dppe),]+ in good yield. Paramagnetism is evident in the broadened NMR spectra. The shows that the hycrystal structure of tr~ns-[TcCl(NNMe~)(dppe)~IPF~ drazido(2-) ligand is bonded as a linear four-electron donor (278). E. COMPLEXES WITH PHOSPHINE AND ARSINE LIGANDS The emerald-green air-stable truns-[TcC1,(PPh3),lis readily prepared in high yield by the reduction of TcO,- with HCl/PPh3 (280).

A variety of seven-coordinate Re analogs of BATOs, uncapped [Re"'C1(cdoH),(cdoH~~],and monocapped [Re"'Cl(cdo)(cdoH),BR] has been prepared. Yields from Re0,- are low but [ReC13(MeCN)(PPh,),] is a suitable starting material. As with Tc, the biscapped Re complexes could not be prepared. Reaction of Mn(OAc),/ cdoH,/(OH),BPh/MeOH, however, gives a high yield of the biscapped six-coordinate [Mnll(cdo)(cdoH),{B(OMe)Ph}~l, in which each cap is covalently bonded to two oxime oxygen atoms (263). A series of cationic [Tc(L)(PR3),1PF,(PR3 = PEt3, PEtzPh, PEtPh, , PPh3)complexes of tetradentate (acac),en ligands and aromatic derivatives has been prepared by substitution/reduction of [TcOCl,I- (2641.

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