Electrochemically-induced isomerization of {(η5-C5H5)Mo(CO)2(μ-SR)}2 (R Me, t-Bu, Ph) complexes. 1H NMR and electrochemical studies. Sythesis and X-ray crystal structure of {(η5-C5H5)Mo(CO)2(μ-S-t-Bu)}2(BF4)2
TL;DR: In this paper, the first geometrical isomerization of thiolato-bridged dimolybdenum complexes induced by the transfer of two electrons at the same potential is reported.
About: This article is published in Journal of Organometallic Chemistry.The article was published on 1986-09-16. It has received 31 citations till now. The article focuses on the topics: Isomerization & Nuclear magnetic resonance spectroscopy.
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TL;DR: A review of electron and proton transfer involving hexacarbonyl and substituted 2Fe2S complexes inspired from the active site of the [Fe]-hydrogenases ([FeFe]H2ases is presented in this paper.
293 citations
TL;DR: In this article, the reduction of Fe2(CO)5LNHC(μ-pdt) was shown to be possible in a single-step, two-electron process at moderate scan rates.
Abstract: The complexes [Fe2(CO)6{μ-SCH2N(R)CH2S}] (R = CH2CH2OCH3, 1a; R = iPr, 1b) and [Fe2(CO)6(μ-pdt)] 2 (pdt = S(CH2)3S) are structural analogues of the [2Fe]H subsite of [FeFe]H2ases. Electrochemical investigation of 1 and 2 in MeCN–[NBu4][PF6] under Ar and under CO has demonstrated that the reduction can be resolved into two one-electron transfer steps by using fast scan cyclic voltammetry. At slow scan rates the reduction of 1 tends towards a two-electron process owing to the fast disproportionation of the anion, while the two-electron reduction of 2 is clearly favoured in the presence of CO. Substitution of a CO ligand in 2 by a N-heterocyclic carbene results in the destabilisation of the anion. Thus, in MeCN–, thf- or CH2Cl2–[NBu4][PF6], the electrochemical reduction of Fe2(CO)5LNHC(μ-pdt)] 3 (LNHC = 1,3-bis(methyl)-imidazol-2-ylidene, 3a; 1,3-bis(2,4,6-trimethylphenyl)-imidazol-2-ylidene, 3b) occurs in a single-step, two-electron process at moderate scan rates; under appropriate conditions this process can be separated into two one-electron steps. Density Functional Theory calculations successfully rationalize the effects of the S-to-S linkage on the electrochemistry of the complexes.
99 citations
TL;DR: The synthesis, reactivity, structures and electrochemistry of dimolybdenum complexes jointly stabilized by cyclopentadienyl and bridging thiolate ligands are reviewed in this article.
62 citations
TL;DR: The first examples of stable, mononuclear 17-electron carbonyl complexes of Mo(III) have been synthesized, isolated, and characterized by IR and EPR spectroscopy as discussed by the authors.
Abstract: The first examples of stable, mononuclear 17-electron carbonyl complexes of Mo(III) have been synthesized, isolated, and characterized by IR and EPR spectroscopy. Oxidation of Cp*MoCl(CO)(PMe3)2 (1; E1/2 = −0.48 V vs Fc/Fc+), Cp*MoCl(CO)(dppe) (2; E1/2 = −0.44 V), and CpMoCl(CO)(dppe) (3; E1/2 = −0.25 V) with Fc+PF6- yields [1]PF6, [2]PF6, and [3]PF6, respectively. The IR stretching vibration of the 17-electron oxidation products are 136−153 cm-1 blue-shifted with respect to the corresponding stretching vibrations of the parent Mo(II) compounds. The room temperature EPR spectra show observable coupling to the Mo and P nuclei and indicate a trans geometry for 1+ and a cis geometry for 2+ and 3+. The four-legged piano stool geometry of 2+ with the phosphines atoms in relative cis positions has been confirmed by a single-crystal X-ray analysis. The X-ray data for [2]PF6·THF are the following: monoclinic, P21/n, a = 13.7394(14) A, b = 20.421(2) A, c = 14.857(2) A, β = 99.119(8)°, V = 4115.8(8) A3, Z = 4, Dx ...
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202 citations
TL;DR: In this paper, a three-pathway isomerization of Ru(dppm)/sub 2/Cl/sub 2 /sub 2 ) was shown to be substitution labile in solvents that can act as ligands while the trans isomer is inert.
Abstract: The complexes cis- and trans-Ru/sup II/(dppm)/sub 2/Cl/sub 2/ (dppm = Ph/sub 2/PCH/sub 2/PPh/sub 2/) have been found to undergo isomerization reactions induced by light, heat, or oxidation to Ru(III). The conversion trans ..-->.. cis occurs thermally while cis ..-->.. trans occurs photochemically apparently by irradiation of the lowest lying d-d transition. Upon chemical or electrochemical oxidation of the cis isomer, the trans isomer of Ru(III) forms quantitatively. The cis isomer was found to be substitution labile in solvents that can act as ligands while the trans isomer is inert. Comparisons of the three-pathway isomerization of Ru(dppm)/sub 2/Cl/sub 2/ are also made with its osmium analogue and with the carbonyl complex (N,N'-Me/sub 2/Im)/sub 2/W(CO)/sub 4/.
109 citations
TL;DR: In this article, the authors describe the composition, composition, and substrate reactions of molybdoenzymes and present the results from the "State of the Art Symposium: Bioinorganic Chemistry", held at the ACS meeting, Miami, 1985.
Abstract: Sources, composition, and substrate reactions of molybdoenzymes. From the "State of the Art Symposium: Bioinorganic Chemistry", held at the ACS meeting, Miami, 1985.
69 citations