| Autor: |
Kefalidis CE; Université de Toulouse et CNRS, INSA, UPS, UMR 5215, LPCNO, 135 Avenue de Rangueil, F-31077 Toulouse, France. laurent.maron@irsamc.ups-tlse.fr., Frey AS, Roe SM, Cloke FG, Maron L |
| Jazyk: |
angličtina |
| Zdroj: |
Dalton transactions (Cambridge, England : 2003) [Dalton Trans] 2014 Aug 07; Vol. 43 (29), pp. 11202-8. Date of Electronic Publication: 2014 Apr 28. |
| DOI: |
10.1039/c4dt00618f |
| Abstrakt: |
Computational studies on the reductive activation of a mixture of CO and NO by the U(iii) complex [U(η-C8H6{Si(i)Pr3-1,4}2)(η-Cp*)], which affords a mixture of [U(η-C8H6{Si(i)Pr3-1,4}2)(η-Cp*)]2(μ-OCN)21 and [U(η-C8H6{Si(i)Pr3-1,4}2)(η-Cp*)]2(μ-O) 2, show that the reaction proceeds via an initial attack of CO on a μ-η(2):η(2) coordinated NO, side-on bridged between two uranium centres. This leads to the formation of the bridging oxo complex 2 and the cyanate radical; coordination of the latter to the starting complex and dimerisation affords 1. The DFT studies also predict the existence of the monocyanate-bridged, mixed valence species [U(η-C8H6{Si(i)Pr3-1,4}2)(η-Cp*)]2(μ-OCN) 3, which has now been experimentally observed. |
| Databáze: |
MEDLINE |
| Externí odkaz: |
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