The effects of solvents on reactivities, kinetics and charge transfer spectra of some transition metal diimine complexes.

摘要

The reaction between Fe(phen)32+ and Nu (Nu = OH-, CN-) in aqueous methanol mixtures was analysed, in terms of H into initial state-transition state contributions. The racemisation of the (-) Fe(phen)32+ cation in aqueous DMSO and aqueous methanol mixtures was analysed, in terms of G, into initial state-transition state contributions. Fe(mppm)32+ was resolved, and the kinetics of racemisation were investigated. Fe(5NO2 phen)32+ was resolved and found to racemise very quickly at 25°C. Ru(5NO2 phen)32+ was resolved, and showed no tendency to racemise at 25°C. Attempts to resolve Fe(btz)32+ and Ru(btz)32+ were unsuccessful. The reactions between Fe(btz)32+ and R (R = OH-, H+, Hg2+, Cd2+, S2,O82-, phen, bipy) are reported. The stability constants of Fe(btz)32+, Agbtz+, Cdbtz2+ and Hgbtz2+ were measured. The solvatochromism of Mo(CO)4 btz, Mo(CO)4 bipym, PNA, DMIA, Fe(btz)2 (CN)2 are reported. The solvatochromism of Mo(CO)4 btz, PNA and DMIA were analysed into ground state-excited state contributions. The structure of Mo(C0)4 btz is described. The solvolysis of Mo(CO)4 btz was analysed in terms of initial state-transition state contributions. The reactions between Mo(CO)4 btz and Q (Q = Hg2+, HgC12, PtC142-, In3+, Cd2+, MeI, PtC12, PPh3, P(OPh)3, Mo(CO)4 (pip)2) are reported. The reactions between Mo(CO)4 (pip)2. and R (R = btz, dt, (btz + bipy), PtC12btz) are reported. The preparation of PtC12btz is described.