A Textbook of Inorganic Chemistry by Friend J.N. (ed.)

By Friend J.N. (ed.)

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R-o-'H L L Me (30) Studies of titanium@)-Schiff base interactions continue. Attempts193to establish a linear correlation between the heat of mixing (Q) of TiC1, and the Schiff bases (30); R = H, p-tolyl, p-Me,CH, pMeO, p-Cl, p-Br, pNO2, or rn-NO& and the change in the C=N stretching frequency, Av(C=N), which occurs on co-ordination and is a measure of the metal-ligand bond strength were unsuccessful, although such a correlation exists for the SnCl, adducts. However, a linear correlation was established between Q and the Hammett substituent constants of R.

L6' Deviations from random scrambling were rationalized on the basis of an electrostatic model. Attempts to prepare metallorganic polymers via thermal condensation between aromatic diols and Ti(L-L),(alkoxy),(L-L = chelate ligand) complexesgave insoluble powders and low molecular weight products. 166Various Ti(L-L),(phenoxy),(L-L = acac, oxalate, or quin) were synthesized but these too had cis octahedral structures. In solution rapid Me group exchange occurs for Ti(acac),(phenoxy),. A dissociative acac bond rupture mechanism was favoured in preference to a twist-type mechanism.

9 D for Ti(S,CNRJ,Cl, (R = Pr’ or Bu’) in benzene solution indicate a cis configuration for these six-co-ordinate complexes. All the Ti(S,CNR),Cl, -,, complexes undergo a fast metal-centred rearrangement and the Ti(S,CNPr~),Cl,-, complexes also undergo isopropyl group exchange. A gear-like mechanism involving rotation about C-N single bonds was proposed for the latter process on the grounds that the activation parameters are virtually independent of co-ordination number. 577(3) A. 61 A) because of the restricted ‘bite’(ca.

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A Textbook of Inorganic Chemistry by Friend J.N. (ed.)
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