Inorganic Electrochemistry. Theory, Practice and Application, 2nd Edition

In order to understand the basic aspects of an electrochemical investigation on inorganic molecules (in its widest meaning, of any molecule which contains at least one metal centre) it must be taken into account that in these molecules the metal-ligand bonds are of the prevailingly covalent type. Since electrochemical techniques allow you to add or remove electrons in a controlled manner, it is conceivable that the addition or removal of electrons inside these molecules can lead to the formation of new bonds or to the breakage of existing bonds. The main aim of this book is to study the effects of such electron addition and removal processes on the molecular frames. The second edition of this classic book has been fully revised and updated and is a straightforward, logical introduction to electrochemical investigations for inorganic chemists. All chapters have been rewritten with new material including: - the addition of reactivity with nitric oxide to the chapter on the reactivity of metal complexes with small molecules - thiolate-protected gold nanoclusters has been added to the chapter on metal-sulfur and metal-carbonyl clusters - a new chapter on the digital simulation of electrochemical responses - a new chapter on the theoretical calculations to explain the nature of the electrochemical activity of metal complexes - new chapters on spectroelectrochemistry and electrochemiluminescence. The book covers every aspect of inorganic electrochemistry - the introduction is followed by chapters on the basic aspects of electrochemistry followed by practical and applicative aspects and ends with full appendices. It is probably the only publication with a simple approach to electrochemical aspects of the topics in inorganic chemistry. Bridging the gap between undergraduate and research-level electrochemistry books, this publication will be a welcome addition to the literature of inorganic chemists. It will also be particularly useful to final year students in chemistry and as background reading for graduates and researchers without adequate electrochemical knowledge to become active in the discipline or who want to collaborate with electrochemists

The redox behavior of 9-nickelafluorenyl sandwich complexes

A collection of nickelocene and cobaltocene analogs with one or two nickelafluorenyl rings has been recently synthesized starting from 9-nickelafluorenyllithium complex. The redox ability of the whole series of derivates has been investigated by electrochemical techniques, and the nature of the frontier orbitals responsible for the electron transfer activity of this class of compounds has been supported by extended Hückel calculations

Isomerism and Redox properties of 1-Ferrocenyl-1,3-butanedionate Complexes

The ferrocenyl diketone [(C5H5)Fe(C5H4)COCH2COCH3] has been used to form neutral metal complexes of the 1-ferrocenyl-1,3-butanedionate ligand [(C5H5)Fe(C5H4)COCHCOCH3](-): the aluminium complex of this ligand, [Al{(C5H5)Fe(C5H4)COCHCOCH3}(3)], has been characterised by H-1 and C-13 NMR as a 2:3 mixture of fac and mer isomers, having C-3 and C-1 molecular symmetry respectively. Electrochemical studies show that each peripheral 1-ferrocenyl-1,3-butanedionate ligand L of both (ML2)-L-II (M = Co, Ni, Cu) and (ML3)-L-III (M = Al, Cr, Mn, Fe) complexes undergoes reversible one-electron oxidation at potential values essentially overlapping each other. This means that the central metal ions prevent any electronic communication between the two or three ferrocene fragments. In addition to these reversible ferrocene-centred oxidations, there are reversible one-electron reductions centred at M for MnL3 and FeL3 (but not for CrL3 or AlL3), but the metal-centre reductions of (ML2)-L-II are irreversible owing to further reactions following reduction. (C) 1998 Elsevier Science Ltd. All rights reserved.</p

Ferrocene-based tris(1-pyrazolyl)borates: a new approach to heterooligometallic complexes and organometallic polymers containing transition metal atoms in the backbone.

Starting from mono- and bifunctional ferrocene-based tris(1-pyrazolyl)borates, a novel route to oligonuclear complexes is presented, which incorporates transition metal centers differing substantially in their chemical nature. Both binuclear organometallics FcB(pz)3MLn (Fc:  ferrocenyl. pz:  1-pyrazolyl. MLn:  Tl, 1-Tl; Mo(CO)3Li, 1-MoLi; Mo(CO)2(η3-methylallyl), 1-Mo; ZrCl3, 1-Zr) and trinuclear complexes 1,1‘-fc[B(pz)3MLn]2 (fc:  ferrocenylene. MLn:  Tl, 2-Tl; Mo(CO)3Li, 2-MoLi; Mo(CO)2(η3-methylallyl), 2-Mo) have been prepared. The trinuclear compound [FcB(4-SiMe3pz)3]2Fe, 1-FeSi, has been investigated as a model system for organometallic coordination polymers, consisting of the bifunctional linker 1,1‘-fc[B(pz)3]22- and transition metal ions Mn+. X-ray crystallography shows 1-Tl to establish a polymeric structure in the solid state, while 1-Mo features the usual tridentate coordination mode of the scorpionate ligand (C25H25BFeMoN6O2; a = 8.756(1) Å, b = 12.154(1) Å, c = 12.927(1) Å, α = 105.26(1)°, β = 102.29(1)°, γ = 105.09(1)°; triclinic space group P1̄; Z = 2). With the exception of 1,2-Tl, the anodic oxidation of the ferrocene moiety is generally reversible; cyclic voltammetry measurements indicate the two Mo centers in 2-Mo and the two Fc moieties in 1-FeSi to be noncommunicating

Redox Control of Light-Induced Cluster-to-Iron Charge Transfer in the Bis(ferrocenylethynyl)-Substituted Hexanuclear Platinum Derivative [Pt6(mu-PBut2)4(CO)4(CC-Fc)2]

Platinum-cluster-to-iron charge transfer complex, FcC≡C[Pt6]C≡CFc [1; Fc = (η-C5H5)Fe(η-C5H4), [Pt6] = [Pt6(μ-PBut2)4(CO)4]2+] was prepd. in good yields by the CuI-catalyzed coupling of two equiv. of ethynylferrocene with the hexanuclear cluster [Pt6(μ-PtBu2)4(CO)4Cl2]. Electrochem. and spectroelectrochem. data of 1 show photoelectrochem. triggered electron transfer from the {Pt6} core to the peripheral ferrocenyl subunits

4-Ethynylpyridine as a bridging moiety in mixed Rh/Re complexes

A paramagnetic, dimeric RhIIIRhII complex of the formula [Rh2(form)4(C≡CC5H4N)] (1) [form = N,N′-di-p-tolylformamidinate; C5H4N = pyridyl (py)] has been synthesized and used as starting material to prepare heterotrimetallic complexes of composition [Rh2(form)4(C≡Cpy){Re(CO)3(bipy)}][OS(=O)2CF3] (2) and [Rh2(form)4(C≡Cpy){Re(CO)3(tbu2bipy)}][OS(=O)2CF3] (3). These complexes have been examined by vibrational spectroscopy, EPR spectroscopy, thermogravimetry and cyclic voltammetry. They are heat-stable and can be handled in air without problems. The observed interactions between the Rh2 and the Re subunits, however, are weak, and a significant charge transfer does not seem to take place