Chemical Bonding and Geometry of Molecules by Ryschkewitsch G.E.

By Ryschkewitsch G.E.

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6 1:1 2:1 3:1 118-131 75-95 20-30 100-140 120-160 65-90 80-115 235-273 150-180 50-60 160-200 220-300 130-170 160-220 408-435 220-260 70-82 4:1 -560 290-330 90-100 340-420 200-240 An example of the use of this method is the hydrolysis of c/i-[Cr(Me cyclam)Cl ]Cl in water at 25°C 2 + 3+ c/s-[Cr(Me cyclam)Cl ] -> c«-[Cr(Me cyclam)(OH ) ] + 2C1" 2 2 2 2 2 2 51 Activation Parameters AHt and ASt Ch. 2] 1 2 1 2 1 The zero time value of A is ca. 125 ohm" c m mol" , Fig. 10, consistent with a 1:1 electrolyte and this value rises to 450 ohm" c m mol' over a period of time indicating loss of the two coordinated chlorides and the formation of a 3:1 electrolyte.

2 χ 10 M. d . 1) The dissociation rates are very sensitive to solvent variation, covering a range of 9 orders of magnitude. Except for (2,1,1) cryptâtes formation rates are all within the range ΙΟΜΟ' M ' s ' . Formation rates in water are much lower than expected. It is suggested that this is due to the Η-bonded interactions between water and the electronegative atoms (O and N) of the ligands. 7. Ch. 6 R a t e constants for dissociation of cryptâtes in various solvents. G. Cox, J. Garcia-Rosas and H.

Swinehart, Progr. Inorg. , 13, 107 (1970). 39. B. H. Wang, J. Am. Chem. Soc, 82, 3498 (1960). 40. D. Berezin, Coordination Compounds of Porphyrins and Phthalocyanines, Chapter 7, Wiley Chichester, 1981. 2 The Kinetic Background INTRODUCTION Kinetic studies are of fundamental importance in any investigation of reaction mechanism. Kinetics may be approached either as a discipline in its own right or as a tool for the elucidation of reaction mechanism. The aim of the present chapter is to discuss some basic practical kinetic techniques which are useful in the diagnosis of reaction mechanism.

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