Photochemistry of (.eta.3-C3H5)Ru(CO)3Br: spectroscopic evidence for the intermediates (.eta.3-C3H5)Ru(CO)2Br and [(.eta.3-C3H5)Ru(CO)2(.mu.-Br)]2
Photochemistry of (.eta.3-C3H5)Ru(CO)3Br: spectroscopic evidence for the intermediates (.eta.3-C3H5)Ru(CO)2Br and [(.eta.3-C3H5)Ru(CO)2(.mu.-Br)]2
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(.eta.3-C3H5)Ru(CO)3Br 的光化学：中间体 (.eta.3-C3H5)Ru(CO)2Br 和 [(.eta.3-C3H5)Ru(CO)2( 的光谱证据
DOI：
10.1021/om00098a022
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发表时间：
1988
期刊：
影响因子：
2.8
通讯作者：
M. Wrighton
中科院分区：
文献类型：
--
作者：
Y. Wuu;M. Wrighton
本文介绍了（/eta//sup 3/-C/sub 3/H/sub 5/）Ru(CO)/sub 3/Br的光化学研究结果。室温下辐照内（/eta//sup 3/- c /sub 3/H/sub 5/）Ru(CO)/sub 3/Br和外（/eta//sup 3/- c /sub 3/H/sub 5/）Ru(CO)/sub 3/Br的平衡混合物，可使外（/eta//sup 3/- c /sub 3/H/sub 5/）Ru(CO)/sub 3/Br的混合物富集。（/eta//sup 3/-C/sub 3/H/sub 5/）Ru(CO)/sub 3/Br在低温基质中辐照表明，主要的光过程是CO的损失。（/eta//sup 3/-C/sub 3/H/sub 5/）Ru(CO)/sub 3/Br在没有反应分子的情况下光解得到的物质经IR、/sup 1/H NMR和质谱鉴定为((/eta//sup 3/-C/sub 3/H/sub 5/)Ru(CO)/sub 2/(/mu/-Br))/sub 2/。((/eta//sup 3/- c /sub 3/H/sub 5/)Ru(CO)/sub 2/(/mu/-Br))/sub 2/与CO反应生成exo-(/eta//sup 3/- c /sub 3/H/sub 5/)Ru(CO)/sub 3/Br热还原为endo-(/eta//sup 3/- c /sub 3/H/sub 5/)Ru(CO)/sub 3/Br。
The authors present here the results of an investigation of the photochemistry of (/eta//sup 3/-C/sub 3/H/sub 5/)Ru(CO)/sub 3/Br. Irradiation of an equilibrium mixture of endo-(/eta//sup 3/-C/sub 3/H/sub 5/)Ru(CO)/sub 3/Br and exo-(/eta//sup 3/-C/sub 3/H/sub 5/)Ru(CO)/sub 3/Br at room temperature in solution results in enrichment of the mixture in exo-(/eta//sup 3/-C/sub 3/H/sub 5/)Ru(CO)/sub 3/Br. Irradiation of (/eta//sup 3/-C/sub 3/H/sub 5/)Ru(CO)/sub 3/Br in a low-temperature matrix demonstrates that the primary photoprocess is loss of CO. Photolysis of (/eta//sup 3/-C/sub 3/H/sub 5/)Ru(CO)/sub 3/Br in the absence of reactive molecules yields a species which they have characterized by IR, /sup 1/H NMR, and mass spectrometry and assigned to be ((/eta//sup 3/-C/sub 3/H/sub 5/)Ru(CO)/sub 2/(/mu/-Br))/sub 2/. ((/eta//sup 3/-C/sub 3/H/sub 5/)Ru(CO)/sub 2/(/mu/-Br))/sub 2/ reacts with CO yielding exo-(/eta//sup 3/-C/sub 3/H/sub 5/)Ru(CO)/sub 3/Br which thermally reverts to endo-(/eta//sup 3/-C/sub 3/H/sub 5/)Ru(CO)/sub 3/Br.