Electrophilic Addition to 2-Aldehyde Complexes of Pentaammineosmium(II): The Formation of Fischer Carbyne Complexes via
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- 作者：Michael L. Spera ; Huiyuan Chen ; Marcus W. Moody ; Maria M. Hill ; and W. Dean Harman
- 刊名：Journal of the American Chemical Society
- 出版年：1997
- 出版时间：December 31, 1997
- 年：1997
- 卷：119
- 期：52
- 页码：12772 - 12778
- 全文大小：302K
- 年卷期：v.119,no.52(December 31, 1997)
- ISSN：1520-5126
文摘
A series of 
mages/gifchars/eta.gif" BORDER=0 >2-aldehyde complexes ofpentaammineosmium(II) of the form[Os(NH3)5(L)](OTf)2(L =formaldehyde (1), acetaldehyde (2),trimethylacetaldehyde (3), benzaldehyde (4), andcrotonaldehyde (5), OTf =trifluoromethanesulfonate) are prepared and characterized.Treatment of these mages/gifchars/eta.gif" BORDER=0 >2-bound aldehyde complexeswithCH3OTf affords Fischer carbyne complexes14-18 with typical yields ranging from25-92%. Protonation (HOTf/MeCN) or methylation (MeOTf/DME) of many of these aldehyde complexesafford O-protonated or O-methylatedmages/gifchars/eta.gif" BORDER=0 >2-aldehydium intermediates, respectively, which overtime convert to the corresponding carbyne complex.Thechemistry of olefin-coordinated mages/gifchars/alpha.gif" BORDER=0>,mages/gifchars/beta2.gif" BORDER=0 ALIGN="middle">-unsaturated aldehyde complexesis also explored.