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Advances in Inorganic Chemistry: Inorganic Reaction by Colin D. Hubbard Rudi Van Eldik

By Colin D. Hubbard Rudi Van Eldik

The Advances in Inorganic Chemistry sequence offers well timed and informative summaries of the present growth in numerous topic components inside of inorganic chemistry starting from bio-inorganic to stable nation reports. This acclaimed serial positive aspects stories written by way of specialists within the region and is an quintessential connection with complex researchers. each one quantity of Advances in Inorganic Chemistry comprises an index, and every bankruptcy is totally referenced. This, the 54th quantity within the sequence maintains this practice supplying entire studies by way of top specialists within the box with the focal point on inorganic and bioinorganic response mechanisms. * the newest quantity during this hugely profitable sequence is devoted to inorganic and bioinorganic response mechanisms* entire studies written through major specialists within the box

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If Ga3+, which is not a transition metal but which is in the same row in the periodic table is added, the activation volumes become even positive (Table IV). 5 cm3 molÀ1) (58,60) for a limiting A mechanism (111). The smaller activation volumes measured for V3+, Cr3+ and especially Fe3+ support the attribution of an Ia mechanism for these cations. A limiting A mechanism for [Ti(H2O)6]3+ was also concluded from computational studies with the Hartree-Fock method (103) and with DFT (124). D. SECOND AND THIRD ROW OCTAHEDRAL COMPLEXES Experimental data for solvent exchange on octahedral second- and third-row transition metal ions are limited to the Ru2+/3+, Rh3+ and Ir3+ and to water and acetonitrile solvents (Table VIII (3,125^129)).

A. DUNAND et al. 54Â10À6 (cis) not obs. 68Â10À6 (cis) not obs. 5Â103 (129) (193) (181) (181) (192) (192) Complex [(H2O)4Rh(m-OH)2Rh(H2O)4]4+ [(H2O)3(OH)Rh(m-OH)2Rh(OH)(H2O)3]4+ a Rate constant for the exchange of a particular coordinated solvent molecule (6). ¢rst-order rate dependence on free solvent concentration. The size of the solvent molecules has an important e¡ect on the lability. Replacing the less sterically hindered [Pd(Me2S)4]2+ by [Pd(Et2S)4]2+ increases the exchange rate constant by more than 400 -fold.

8 Id Id Id D and Id D D Ref. (254) (254) (255) (254) (254) (254) Six-coordinate ionic radii from Ref. (255). First-order rate constant for the exchange of a particular coordinated solvent molecule (6). 7 ^ ^ ^ D, Id D, Id D, Id D, Id D, Id D, Id Adapted from Refs. (56,257^259 ). a Six-coordinate ionic radii from Ref. (255). b First-order rate constant for the exchange of a particular coordinated solvent molecule (6). 2 for europium(II) (228). The water exchange rate measured on the divalent europium aqua ion is the fastest ever measured by 17O NMR (Table XVI) (2).

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