Syntheses, characterization, and magnetic studies of copper(II) complexes with the ligand N,N,N',N'-tetrakis(2-pyridylmethyl)-1,3-benzenediamine (1,3-tpbd) and its phenol derivative 2,6-bis[bis(2-pyridylmethyl)amino]-p-cresol] (2,6-Htpcd).

The copper(II) complexes [Cu(4)(1,3-tpbd)(2)(H(2)O)(4)(NO(3))(4)](n)(NO(3))(4n)·13nH(2)O (1), [Cu(4)(1,3-tpbd)(2)(AsO(4))(ClO(4))(3)(H(2)O)](ClO(4))(2)·2H(2)O·0.5CH(3)OH (2), [Cu(4)(1,3-tpbd)(2)(PO(4))(ClO(4))(3)(H(2)O)](ClO(4))(2)·2H(2)O·0.5CH(3)OH (3), [Cu(2)(1,3-tpbd){(PhO)(2)PO(2)}(2)](2)(ClO(4))(4) (4), and [Cu(2)(1,3-tpbd){(PhO)PO(3)}(2)(H(2)O)(0.69)(CH(3)CN)(0.31)](2)(BPh(4))(4)·Et(2)O·CH(3)CN (5) [1,3-tpbd = N,N,N',N'-tetrakis(2-pyridylmethyl)-1,3-benzenediamine, BPh(4)(-) = tetraphenylborate] were prepared and structurally characterized. Analyses of the magnetic data of 2, 3, 4, and [Cu(2)(2,6-tpcd)(H(2)O)Cl](ClO(4))(2) (6) [2,6-tpcd = 2,6-bis[bis(2-pyridylmethyl)amino]-p-cresolate] show the occurrence of weak antiferromagnetic interactions between the copper(II) ions, the bis-terdentate 1,3-tpbd/2,6-tpcd, µ(4)-XO(4) (X = As and P) µ(1,2)-OPO and µ-O(phenolate) appearing as poor mediators of exchange interactions in this series of compounds. Simple orbital symmetry considerations based on the structural knowledge account for the small magnitude of the magnetic couplings found in these copper(II) compounds.

Syntheses, emission properties and intramolecular ligand exchange of zinc complexes with ligands belonging to the tmpa family.

The zinc complexes [(L1)(2)Zn(MeOH)(2)](OTf)(2), [(L1)ZnCl(2)], [(L2)ZnCl(2)], [(L2)Zn(OTf)(H(2)O)]OTf and [(Me-bispic)ZnCl(2)] of the ligands N-[(2-pyridyl)methyl]-2,2'-dipyridylamine (L1), N-[bis(2-pyridyl)methyl]-2-pyridylamine (L2) and N-methyl-[bis(2-pyridyl)methyl]amine (Me-bispic) were synthesised and characterised. The first copper(I) complexes of the ligands L1 and L2 were also synthesised and structurally characterised. [(L1)ZnCl(2)] showed unexpected fluxional behaviour in solution and revealed an interesting intramolecular ligand exchange mechanism in the coordination sphere of the zinc ion. Furthermore, strong blue emission was observed under UV-light excitation.

Reinvestigation of the formation of a mononuclear Fe(III) hydroperoxido complex using high pressure kinetics.

Previous stopped flow kinetic experiments suggested an interchange associative mechanism for the ligand substitution reaction, [Fe(bztpen)(OMe)](2+) + H(2)O(2)--> {[Fe(bztpen)(OMe)(HOOH)](2+)}(++)--> [Fe(bztpen)(OOH)](2+) + MeOH (bztpen = N-benzyl-N, N',N'tris(2-methylpyridyl)-ethylenediamine). Thus a seven-coordinate transition state containing both the leaving methoxide and the incoming hydrogen peroxide ligands was proposed. On the basis of high pressure kinetic data we can now conclude that this is not the case since the rate of the reaction is independent of pressure for the formation of the purple low spin transient hydroperoxido complex, [Fe(bztpen)(OOH)](2+). [Fe(bztpen)(OOH)](2+) has so far proved to be too short-lived for solid state isolation. As part of our ongoing pursuit of this elusive species we have structurally characterised the nitrosyl and acetate iron(II) complexes, [Fe(bztpen)(NO)](OTf)(2) and [Fe(bztpen)(OAc)](BPh(4)), as well as the air stable Co(II) complexes [Co(bztpen)Cl)]BF(4), [Co(metpen)Cl]SbF(6) and [Co(bztpen)(OAc)]BPh(4). We did not realise our aim of accessing stable Co(III) hydroperoxido or peroxido complexes by reaction of the cobalt complexes with H(2)O(2).