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A new efficient method for the synthesis of dicompartmental ligands enalH 2 8 and of tnalH2, 10 is described. This method is essentially a concise one-step route via the Mannich condensation, from 4-methyl 2-formylphenol and paraformaldehyde with appropriate amines. A series of macrocyclic heterobimetallic complexes of type [Mc(tntnam)M o](PF6)n and [Mc'(tntnim)Ni](PF 6)n where Mc = Co(III) and Zn(II), Mc ' = Co(II), Co(III) and Zn(II) and Mo = Ni(II), Cu(II) and Zn(II) have been synthesized and characterized. The macrocyclic ligands tntnim 12 and tntnam 13 contain two geometrically distinct 6-coordinate (closed-site) and 4-coordinate (open-site) compartments which are bridged by phenolic oxygens. The heterobimetallic complexes with Zn(II) or Ni(II) in the open-site are primarily formed as 5-coordinate with a chloride ion as a fifth ligand; the latter can be removed by Ag+ ion. The 1H NMR and 13C NMR of diamagnetic complexes and [Co(tntnam)ZnCl](PF6)2, 27 and [Co(tntnam)Zn](PF6)3, 28 demonstrate that the expected trans pyridine structures are formed. Solution magnetic moments of heterobimetallic complexes indicate that all Co(III) ions are spin paired, but the Ni(II) ions are spin free. The electronic absorption and emission spectra and redox couples are reported. The crystal structures of [Zn(tntnim)NiCl]PF 6C2H5OH, 16, [Zn(tntnam)Ni](PF 6)2, 22, [Zn(tntnam)Cu](PF6) 2, 23, and [Co(tnmam)Ni(H2O)](PF6) 34H2O, 25 were determined. The crystal structures demonstrate that the expected 'trans' pyridine structures are formed. Photoreactivity of heterobimetallic complexes towards molecular oxygen showed that, in spite of sensitivity of these complexes to molecular oxygens no singlet molecular oxygen, O2 (1[Delta]g), or peroxide species were generated as a result of irradiation with visible light. A series of acyclic ligands analogous to the dialdehyde ligand enalH 2, but containing different ligating groups instead of the aldehyde moieties were prepared. These include dial.
Organometallic chemistry is an interdisciplinary science which continues to grow at a rapid pace. Although there is continued interest in synthetic and structural studies the last decade has seen a growing interest in the potential of organometallic chemistry to provide answers to problems in catalysis synthetic organic chemistry and also in the development of new materials. This Specialist Periodical Report aims to reflect these current interests reviewing progress in theoretical organometallic chemistry, main group chemistry, the lanthanides and all aspects of transition metal chemistry. Specialist Periodical Reports provide systematic and detailed review coverage of progress in the major areas of chemical research. Written by experts in their specialist fields the series creates a unique service for the active research chemist, supplying regular critical in-depth accounts of progress in particular areas of chemistry. For over 80 years the Royal Society of Chemistry and its predecessor, the Chemical Society, have been publishing reports charting developments in chemistry, which originally took the form of Annual Reports. However, by 1967 the whole spectrum of chemistry could no longer be contained within one volume and the series Specialist Periodical Reports was born. The Annual Reports themselves still existed but were divided into two, and subsequently three, volumes covering Inorganic, Organic and Physical Chemistry. For more general coverage of the highlights in chemistry they remain a 'must'. Since that time the SPR series has altered according to the fluctuating degree of activity in various fields of chemistry. Some titles have remained unchanged, while others have altered their emphasis along with their titles; some have been combined under a new name whereas others have had to be discontinued. The current list of Specialist Periodical Reports can be seen on the inside flap of this volume.