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The Reactions of Carbon Monoxide with the Series of Dirhenium Species (re2cl4(pme2ph)4)n+ (n = 0, 1, 2) Possessing Rhenium-rhenium Bond Orders of 4, 3.5 and 3
| Content Provider | Semantic Scholar |
|---|---|
| Author | Dunbar, Kim R. Walton, Richard A. |
| Copyright Year | 1984 |
| Abstract | The complexes [ReZCl,(PMe,Ph),](PF6),, where n = 0, 1 or 2, which possess Re-Re multiple bonds of orders 3, 3.5 and 4, respectively, react with carbon monoxide in 2-methoxyethanol to afford the reductive cleavage product ReCl(CO)JPMezPh), in high yield. In other solvents (ethanol and toluene), these reactions are complicated by competing side reactions which can result in redox chemistry at the dirhenium units without the incorporation of CO into the products. The reactions in ethanol and toluene lead to the formation of RezC1,(PMe,Ph)J, Re,Cl,(PMeZPh)Z, trans-ReC14(PMezPh)z, ReC1(C0)z(PMe2Ph)a and/or ReC13(CO)(PMe,Ph),, in addition to ReCl(CO),(PMe,Ph),, depending upon the reaction conditions. The electrochemical properties of the carbonyl containing products ReC1(CO)z(PMezPh)S, ReCl(CO),(PMe2Ph)2 and ReC13(CO)(PMe,Ph),, as well as those of the previously described rhenium(H) dicarbonyl complex ReClz(C0)2(P-n-Pr,),, have been studied using the cyclic voltammetry technique. As a logical development of this work, we have investigated the reactions of the series of complexes ReZCl,,(PMe2Ph)4, [RezC14(PMe2Ph)4]PF6 and [ReZC14(PMe2Ph)a](PF6)2 with carbon monoxide. These molecules, which we have recently isolated and structurally characterized [3], possess bond orders of 3, 3.5, and 4, the oxidations being achieved by sequential loss of electrons from the 6* molecular orbital of RezC14(PMezPh),. The purpose of our investigation was two-fold. First, we were interested in comparing the results with those reported in the earlier study in which the ReZC14(PR3)4 starting materials contained the trialkyl phosphines PEt, or P-n-Pra [3], as well as noting any reactivity differences which might exist between members of the series in which the Re-Re bond order varies from 3 to 3.5 to 4. Secondly, we were interested in exploring by electrochemistry the redox chemistry of the carbonyl products so obtained, with the objective of assessing what effect replacing a phosphine ligand with a carbon monoxide ligand would have on the properties of the metal center. |
| File Format | PDF HTM / HTML |
| DOI | 10.1002/chin.198446293 |
| Alternate Webpage(s) | http://www.chem.tamu.edu/rgroup/dunbar/Publications/1984-2.pdf |
| Alternate Webpage(s) | https://doi.org/10.1002/chin.198446293 |
| Volume Number | 15 |
| Language | English |
| Access Restriction | Open |
| Content Type | Text |
| Resource Type | Article |