Electrochemical and IR/UV-Vis Spectroelectrochemical Studies of fax-[MnX)(CO)3(iPr-DABGeneral rights It is not permitted to download or to forward/distribute the text or part of it without the consent of the author(s) and/or copyright holder(s), other than for strictly personal, individual use, unless the work is under an open content license (like Creative Commons). Disclaimer/Complaints regulationsIf you believe that digital publication of certain material infringes any of your rights or (privacy) interests, please let the Library know, stating your reasons. In case of a legitimate complaint, the Library will make the material inaccessible and/or remove it from the website. Please Ask the Library: http://uba.uva.nl/en/contact, or a letter to: Library of the University of Amsterdam, Secretariat, Singel 425, 1012 WP Amsterdam, The Netherlands. You will be contacted as soon as possible. The title complexes [Mn(X)(CO) 3 (iPr-DAB)] n (n ) 0, X ) Br; n ) +1, X ) donor solvent) undergo a two-electron reduction according to an ECE sequence. The chemical step (C) involves prompt dissociation of the X ligand from the primary one-electron reduction product, followed by instantaneous one-electron reduction of the five-coordinate transient [Mn(CO) 3 -(iPr-DAB)] • producing the anion [Mn(CO) 3 (iPr-DAB)] -. The latter complex remains rather stable at T < 190 K, whereas at higher temperatures it undergoes an electron-transfer reaction with the parent complexes producing the dimer [Mn(CO) 3 (iPr-DAB)] 2 (the second C step in the overall ECEC sequence). The rate of this reaction decreases in the order THF • , is probably only a minor alternative route. In the presence of excess P(OMe) 3 , the principal oxidation product is the cation [Mn{P(OMe) 3 }(CO) 3 (iPr-DAB)] + . The fivecoordinate anions [Mn(CO) 3 (R-diimine)] -can be regarded as strongly π-delocalized complexes with the negative charge equally distributed over the R-diimine and CO ligands. The intriguing mechanism of their photochemical formation from fac-[Mn(Br)(CO) 3 (R-diimine)] at low temperatures has been rectified on the basis of this (spectro)electrochemical study. Download date: 13 May 2018 Electrochemical and IR/UV-Vis Spectroelectrochemical Studies of fac-[Mn(X)(CO)

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The reduction of the indenyl complex [Rh(η(5) -C9 H7 )(η(4) -cod)] has been investigated in the context of structural effects induced by the transfer of one electron. The reduction of this complex occurs in two steps, leading first to the radical anion and then to the highly frangible dianion. Both species eliminate the indenyl anion. In the presence of free cyclooctadiene, the related cleavage leading to the indenyl anion and bis-cyclooctadiene rhodium fragments now follows a Michaelis-Menten-type mechanism involving precoordination of one extra COD ligand to the initial radical anion. These results suggest the modification of the hapticity of the indenyl ligand in connection with 17- and 19-electron metalcentered intermediates.