摘要:

A ubiquitous reaction in transition metal chemistry is electron transfer1,2deriving from the variable valence capability of the metal center. When the coordinated ligand has one or more potentially labile protons, electron transfer at the metal (M)mayproceed with symbiotic proton transfer at the ligand (L), Fig. 1. Such a coupled transfer will be called3an electroprotic reaction. An important extension of Fig. 1 can be the transfer of externally added redox equivalents to the ligand via the metal thereby effecting a metal-catalyzed electroprotic transformation of the ligand. The scope of electroprotic phenomena is obviously wide and spans many reactions in chemistry and biology. This Comment has the limited objective of recounting some of our personal experiences in this fascinating field which we gained in the course of our dealing with the synthetic chemistry and redox activity of multiple oxidation states of copper, nickel, ruthenium, and molybdenum.

ISSN:0260-3594    

DOI:10.1080/02603598508072249

出版商:Taylor & Francis Group    

年代:1985

数据来源: Taylor

摘要:

1,2-azaborolinyl systems (Ab) are derived from the well-known C5H5ring (Cp) by substitution of two C atoms by the isoelectronic BN group. Like Cp, the Ab rings form a variety of sandwich compounds with transition metals. The BN-perturbation causes various structural consequences in the complexes. Due to the prochiral character of the C3BN ring, diastereoisomers are formed. Depending on the electron configuration of the metal, slip distortions are observed. Electron-rich metals such as Co or Ni avoid contact with the donor atom N, electron-poor elements like Ti or V avoid contact with the acceptor B. 1,2-azaborolinyl sandwich complexes can therefore act as model compounds to study the metal behavior in sandwich structures depending on the electron configuration.

ISSN:0260-3594    

DOI:10.1080/02603598508072250

出版商:Taylor & Francis Group    

年代:1985

数据来源: Taylor

摘要:

The incorporation of a transition metal ion into a poly-aza macrocyle favors the access to unusually high oxidation states (e.g. NiIII, CuIII). The tendency to stabilize trivalent cations, which is expressed by the value of the potential of the MIII/MIIIredox couple, is regulated by the structural features of the macrocycle (ring size, number and type of the donor nitrogen atoms). In general, formation of trivalent complexes is favored by strong equatorial interactions and the CuII/CuIIIoxidation process profits from the ligand-field contribution to a larger extent than does the corresponding NiII/NiIIIprocess. The solvent may profoundly influence the MIII/MIIIredox change through axial coordination of one of the redox-active macrocyclic complexes.

ISSN:0260-3594    

DOI:10.1080/02603598508072251

出版商:Taylor & Francis Group    

年代:1985

数据来源: Taylor

摘要:

This is a scanned image of the original Editorial Board page(s) for this issue.

ISSN:0260-3594    

DOI:10.1080/02603598508072248

出版商:Taylor & Francis Group    

年代:1985

数据来源: Taylor