By A. G. Sykes
Advances in Inorganic Chemistry provides well timed and informative summaries of the present development in quite a few topic parts inside of inorganic chemistry starting from bio-inorganic to reliable kingdom experiences. Thisacclaimed serial gains studies written by way of specialists within the zone and is an quintessential 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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Extra info for Advances in Inorganic Chemistry, Vol. 41
The bridging 0x0 ligand appears to be in the hydroxy form, consistent with a Tc(1V) oxidation state (373). Raman spectroscopy of Tc-MeC(OH)(PO,), prepared by BH,- reduction, however, indicates the presence of T-0 and O=Tc=O cores (375) and thus of Tc(V) components in this preparation. D. COMPLEXES WITH SCHIFF BASEAND OTHER NITROGEN LIGANDS A number of Schiff base complexes have been prepared by substitution of [TcCl6I2-or [TcCI,(PP~,)~] (376,269). 7 BM, consistent with a d3 configuration (379).
The crystal structure of the tetramethylben- 44 JOHN BALDAS zenethiolato complex, [Tc(tmbt),(MeCN),], reveals trigonal-bipyramidal geometry, with the two MeCN ligands in the axial positions and the three S atoms in the equatorial plane, with the bulky aryl groups arranged two above and one below this plane. The orientation of the aryl rings observed in the crystal structure is shown by the 'H NMR spectra to persist in solution. The [Tc(tmbt),L,] (L = MeCN, py) complexes can be oxidized to TcW) 0x0 compounds by oxygen atom transfer from dmso and other oxygen donors, and [TcvO(tmbt),(py)] may be reduced to [Tc(tmbt),(PEt,),I by PEt3.
The air-stable biddiazenido) [TcC1(NzAr),(PPh3),lcomplexes are formed by the reaction of [TcVOC1,l- or [TcC~,(PP~,)~I with excess ArNHNH, in alcoholic solution or directly from TcO,- (277, 278, 140). Organodiazenido ligands most commonly bond in the singly bent, three-electron-donor mode with the doubly bent, one-electron-donor mode much less com(X = C1, Br) (22) mon. 7(7)"for X = Br and the same essentially linear arrangement for X = C1 (277, 140). 38 JOHN BALDAS PPh, (22) f singly bent 3-electron donor doubly bent l-electron donor The bond distances indicate extensive delocalization and multiple bonding in the -NNAr moieties together with significant Tc backbonding.