Synthesis, Structure, and Reactivity of Mononuclear Re(I) Oximato Complexes
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- 作者：Luciano Cuesta ; Miguel A. Huertos ; Dolores Morales ; Julio Pé ; rez ; Lucí ; a Riera ; Ví ; ctor Riera ; Daniel Miguel ; Amador Mené ; ndez-Velá ; zquez ; Santiago Garcí ; a-Granda
- 刊名：Inorganic Chemistry
- 出版年：2007
- 出版时间：April 2, 2007
- 年：2007
- 卷：46
- 期：7
- 页码：2836 - 2845
- 全文大小：268K
- 年卷期：v.46,no.7(April 2, 2007)
- ISSN：1520-510X
文摘
Complexes [Re(ONCMe2)(CO)3(bipy)] (1) and [Re(ONCMe2)(CO)3(phen)] (2), synthesized by reaction of the respectivetriflato precursors [Re(OTf)(CO)3(N-N)] (N-N = bipy, phen) with KONCMe2, feature O-bonded monodentate oximatoligands. Compound [Re(CO)3(phen)(HONCMe2)]BAr'4 (3), with a monodentate N-bonded oxime ligand, was preparedby reaction of [Re(OTf)(CO)3(phen)], HONCMe2, and NaBAr'4. Deprotonation of 3 afforded 2. The oximato complexesreacted with p-tolylisocyanate, p-tolylisothiocyanate, maleic anhydride, and tetracyanoethylene, affording the productsof the insertion of the electrophile into the Re-O bond, compounds 4-7. One representative of each type ofcompound was fully characterized, including single-crystal X-ray diffraction. The reactions of 1 and 2 withdimethylacetylenedicarboxylate were found to involve first an insertion as the ones mentioned above but followedby incorporation of water, loss of acetone, and formation of the charge-separated neutral amido complexes 9 and10. The structure of 9 and 10 was determined by X-ray diffraction, and key features of their electronic distributionwere studied using a topological analysis of the electron density as obtained from the Fourier map.