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

By A. G. Sykes

Advances in Inorganic Chemistry provides well timed and informative summaries of the present development in a number of topic parts inside of inorganic chemistry starting from bio-inorganic to sturdy country stories. Thisacclaimed serial gains studies written by way of specialists within the region and is an imperative connection with complicated researchers. every one quantity of Advances in Inorganic Chemistry includes an index, and every bankruptcy is absolutely referenced.

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The force constants for all the [TcX,I'- complexes have been determined (334),and the IR and Raman spectra of the 10 [TcCl,,Br,-, 1'- ( n = 0-6) species, including the pure geometrical isomers, at 80 K have been completely assigned and supported by normal coordinate analysis. Due to the C1< Br truns influence, the force constants indicate that in asymmetric C1'-Tc-Br' axes the Tc-Br' bonds are strengthened by on average 6% and the Tc-C1' bonds weakened by 10% relative to symmetric Br-Tc-Br and C1-Tc-C1 axes, respectively (331).

5 (227). Treatment product obtained may in fact be [(q5-C5Me5)TcVI1O31 of [Tc1(C5Me5)(CO>,1 with Br,/CF,COOH gives [ T c ( C ~ M ~ ~ ) ( C Oas )~B~~I a mixture of cis- and trans-isomers (100). 6. C. ~H~O prepared by the reaction of (NH,)2[Tc'VI,l with KCN in methanol under nitrogen. Raman and IR spectra indicate a pentago- COORDINATION CHEMISTRY OF TECHNETIUM 31 nal-bipyramidal structure symmetry) both in the solid state and in solution. Seven-coordinate isonitrile complexes of the type [Tc(CNR)~X](PF~)~ (X = C1, Br) are formed by the oxidative addition of chlorine or bromine to the six-coordinate [Tc'(C"),]+ (1211.

Of great importance and synthetic utility are the stable complex halides [TcX,I2-. Salts of the bright yellow chloro complex [TcC1,I2- are best prepared by prolonged reflux of Tc0,- in concentrated HC1 in order to ensure complete reduction of the initially formed [TcVOCl,l-. Concentrated HBr rapidly yields the red [TcBr,I2-, whereas the deep purple [TcI,12- may be prepared by ligand exchange of the chloro and bromo complexes with HI (26, 27, 328). All eight possible mixed [TcC1,Br6-,,]'- (n = 1-5) complexes have been separated by ion-exchange chromatography.

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