Formation of Ru(NH3)5N22+ in aqueous solution by direct action of molecular nitrogen

Harrison, David; Taube, Henry

doi:10.1021/ja00998a038

Cited by 82 publications

(20 citation statements)

References 0 publications

Supporting

Mentioning

Contrasting

Order By: Relevance

“…The [Ru(NH 3 ) 5 Cl] 2+ intermediate is synthetically versatile and a wide range of ligands have been explored. One of the most well known examples is the first complex of dinitrogen, [Ru(NH 3 ) 5 N 2 ] 2+ reported by Allen and Senoff in 1965 [144,145]. Taube won the Nobel Prize in 1983 for his studies of electron transfer using the mixed valence pyrazine-bridged dinuclear complex [Ru(NH 3 ) 5 pzRu(NH 3 ) 5 ] 5+ otherwise known as the Creutz-Taube complex [146].…”

Section: Redox Species Used For Electrochemical Determination Of Kmentioning

confidence: 99%

Electrochemistry of redox-active self-assembled monolayers

Eckermann

Feld

Shaw

et al. 2010

Coordination Chemistry Reviews

530

492

View full text Add to dashboard Cite

Redox-active self-assembled monolayers (SAMs) provide an excellent platform for investigating electron transfer kinetics. Using a well-defined bridge, a redox center can be positioned at a fixed distance from the electrode and electron transfer kinetics probed using a variety of electrochemical techniques. Cyclic voltammetry, AC voltammetry, electrochemical impedance spectroscopy, and chronoamperometry are most commonly used to determine the rate of electron transfer of redoxactivated SAMs. A variety of redox species have been attached to SAMs, and include transition metal complexes (e.g., ferrocene, ruthenium pentaammine, osmium bisbipyridine, metal clusters) and organic molecules (e.g., galvinol, C 60 ). SAMs offer an ideal environment to study the outer-sphere interactions of redox species. The composition and integrity of the monolayer and the electrode material influence the electron transfer kinetics and can be investigated using electrochemical methods. Theoretical models have been developed for investigating SAM structure. This review discusses methods and monolayer compositions for electrochemical measurements of redox-active SAMs.

show abstract

Section: Redox Species Used For Electrochemical Determination Of Kmentioning

confidence: 99%

Electrochemistry of redox-active self-assembled monolayers

Eckermann

Feld

Shaw

et al. 2010

Coordination Chemistry Reviews

530

492

View full text Add to dashboard Cite

show abstract

“…By then the great capacity of Ru(NH3)f + for backbonding had begun to be appreciated. The observation that N2 (which had been used to exclude air) reacts with [Ru(NH3)5(H20)] 2+ to produce [Ru(NH3)5(N2)] 2+ and [(NH3)5Ru(N2)Ru-(NH3)5] 4+ further demonstrated the great capacity of [Ru(NH3)5(H20)] 2+ for π backbonding (26,27).…”

Section: Mechanisms Of Electron Transfer With Extended Bridging Groupsmentioning

confidence: 99%

“…But the fact that [Ru(NH3)5(N2)] 2+ would be produced also by the reaction of [Ru(NH3)5(H20)] 2+ and N2 in water nevertheless came as a surprise to me. This discovery was made in an experiment in which Harrison deliberately monitored the spectrum of a solution of [Ru(NH3)5(H20)] 2+ (which was pre pared by reducing the corresponding Ru(III) complex by Zn/Hg under argon) while it was bubbled with N2 (26,27). Without invoking the backbonding capacity of [Ru(NH3)5(H20)] 2+ , it would be difficult to understand the replace ment of a good dipole, H20, from the coordination sphere of a cation by the nonpolar N2, and this discovery was powerfully educational.…”

Section: Mechanisms Of Electron Transfer With Extended Bridging Groupsmentioning

confidence: 99%

From Electron Transfer Reactions to the Effects of Backbonding

Taube

1997

Advances in Chemistry

View full text Add to dashboard Cite

The initial motivation for extending the chemistry of ruthenium ammines was to provide new reagents for research on electron transfer reactions. Quite early in pursuing the preparative chemistry, an unexpected capac -ity of Ru(II) for backbonding was uncovered, and the systematic investi -gation of its influence on physical and chemical properties became a goal in its own right. The new directions led to the discovery of a num -ber of novel reactions, which in some cases led to novel products. The research has provided documentation of the effect of backbonding on ligand-to-metal charge transfer, ligand-metal distances, the intensities of infrared absorption by π-acceptor ligands, the acid-base properties of such ligands, the properties of co-ligands exerted by the electronic-with -drawing power of π-acceptor ligands, and on Ru(III)/Ru(II) redox potentials and enthalpies of complex formation. Some early results, which demonstrate the superior capacity of the osmium ammines to engage in backbonding, are also described. ONE OF THE THEMES OF MY EARLY RESEARCH at Stanford, begun late in1961, was the investigation of the mechanisms of substitution reactions of metal complexes by the application of isotope effects, mainly of oxygen. For example, we carried out kinetic and tracer studies in the alkaline hydrolysis of [Co(NH3)5(02CCF3)] 2+ (I) and attempted to generate intermediates such as might be implicated in SN1 mechanisms (e.g., we hoped to generate [Co(NH3)5] 3+ by the nitrosation of [CoiNH^N^P) (2). Mechanisms of Electron TransferThe major emphasis of the research in my group, however, was the investiga tion of the mechanisms of electron transfer reactions. In key experiments done

show abstract

“…The complexes [RuN^NH,)^ were also obtained when all the ligands, except nitrogen, were substituted by ammonia 40 in the non-saltlike complexes RuN 2 Cl2(H 2 O)THF (see p.361)[THF = tetrahydrofuran (Ed. of Translation)], by passing nitrogen 41 into an aqueous solution of [Ru(NH 3 ) 5 H 2 O]Cl 2 , and by the action of ammonia 42 and zinc dust on RuCl 3 .3H 2 O.…”

Section: Synthesis and Chemical Properties Of Nitrogenylsmentioning

confidence: 99%

Complexes of Molecular Nitrogen

Borod'ko¹,

Шилов²

1969

Russ. Chem. Rev.

View full text Add to dashboard Cite

The review deals with problems associated with the formation and structure of complexes of molecular nitrogen with transition metal compounds, metals, and other active species. Nitrogen interacts very weakly with acceptors of the type BF 3 but is capable of forming more stable systems (of the type of diazo-compounds) with species having both acceptor and donor properties (CH 2 , CH, 0). On the surface of metals (nickel, palladium, platinum), nitrogen forms complexes with the linear configuration of the fragment M-N=N. A large number of stable complexes (nitrogenyls), also with a linear configuration of the M-N=N fragment and analogous to the carbonyls and diazo-compounds, have been obtained recently with compounds of iron(ll), ruthenium(ll), osmium(ll), cobalt(l), rhodium(l), iridium(l), and nickel(O). In addition, dinitrogenyl compounds L n M(N 2 ) 2s and dinuclear complexes Μ-ΝΞΝ-Μ are known. In nitrogenyl compounds nitrogen behaves as a π-electron acceptor ligand and therefore donor ligands stabilise the M-N 2 bond in the complex and acceptor ligands weaken it. The method of synthesis of nitrogenyl complexes, their properties, and the mechanism of their formation have been examined. The possibility of the involvement of dinuclear complexes in nitrogen fixation under mild conditions is discussed. The bibliography includes 121 references. CONTENTS

show abstract

Formation of Ru(NH3)5N22+ in aqueous solution by direct action of molecular nitrogen

Cited by 82 publications

References 0 publications

Electrochemistry of redox-active self-assembled monolayers

Electrochemistry of redox-active self-assembled monolayers

From Electron Transfer Reactions to the Effects of Backbonding

Complexes of Molecular Nitrogen

Contact Info

Product

Resources

About