caa a22 4500 465776035 CHVBK 20180323111942.0 cr unu---uuuuu 170327e19901001xx s 000 0 eng 10.1007/BF01177468 doi (NATIONALLICENCE)springer-10.1007/BF01177468 Kinetics of solvolysis and cyanide attack at 2-benzoylpyridine-iminemolybdenum(0) tetracarbonyl and related compounds [Elektronische Daten] [Razak Ali, Michael Blandamer, John Burgess] Summary: The kinetics of reaction of [Mo(CO)4(bpami)], where bpami is the Schiff base derived from 2-benzoyl pyridine and ammonia, with cyanide in several solvents show parallel solvolysis and cyanide attack. Rate laws and activation parameters are consistent with an associative mechanism for the predominant pathway, cyanide attack. From kinetic and solubility measurements it is possible to analyse solvent effects on reactivity for these reactions into initial state and transition state contributions. Rate constant trends in binary mixtures of non-aqueous solvents can be understood in terms of preferential solvation of the molybdenum compound and of cyanide. Finnlly, ligand effects on reactivity have been established for a number of [Mo(CO)4(diimine)] complexes; over a 5×104 times range in rate constants for cyanide attack there is a marked correlation of reactivity with MLCT frequencies for the metal to diimine charge-transfer band. Chapman and Hall Ltd., 1990 Ali Razak Chemistry Department, University of Leicester, LE1 7RH, Leicester, U.K. aut Blandamer Michael Chemistry Department, University of Leicester, LE1 7RH, Leicester, U.K. aut Burgess John Chemistry Department, University of Leicester, LE1 7RH, Leicester, U.K. aut Transition Metal Chemistry Kluwer Academic Publishers 15/5(1990-10-01), 388-393 0340-4285 15:5<388 1990 15 11243 https://doi.org/10.1007/BF01177468 text/html Onlinezugriff via DOI 1 research-article jats NATIONALLICENCE 856 40 https://doi.org/10.1007/BF01177468 text/html Onlinezugriff via DOI NATIONALLICENCE 700 1- Ali Razak Chemistry Department, University of Leicester, LE1 7RH, Leicester, U.K aut NATIONALLICENCE 700 1- Blandamer Michael Chemistry Department, University of Leicester, LE1 7RH, Leicester, U.K aut NATIONALLICENCE 700 1- Burgess John Chemistry Department, University of Leicester, LE1 7RH, Leicester, U.K aut NATIONALLICENCE 773 0- Transition Metal Chemistry Kluwer Academic Publishers 15/5(1990-10-01), 388-393 0340-4285 15:5<388 1990 15 11243 Metadata rights reserved Springer special CC-BY-NC licence nationallicence BK010053 XK010053 XK010000 NATIONALLICENCE NATIONALLICENCE NL-springer