The fragmentation was studied further with nanosecond time-resolved UV–Vis and IR spectroscopy and was found to proceed via the initial formation of a triosmium photoproduct with a lifetime of about 100 ns in hexane. From the spectroscopic data we infer that this intermediate has a coordinatively unsaturated open-triangle structure with two bridging carbonyl groups, one bridging the split (CO) 4 OsOs(CO)
摘要详细研究了[Os 3(CO)10(二烯)]簇(二烯=顺式-
1,3-丁二烯,
1,3-环己二烯)的光
化学性质。在近紫外线照射下发生光碎裂,得到单核[Os(CO)3(二烯)]。通过与CO或与烯烃的低温反应捕获第二个裂解产物[Os 2(CO)7],以生产双核络合物[Os 2(CO)7(L)2](L = CO,
乙烯, 1-
辛烯)。使用纳秒级时间分辨的UV-Vis和IR光谱对碎片进行了进一步研究,发现该碎片是通过初始形成a光产物而进行的,该photo产物在己烷中的寿命约为100 ns。从光谱数据可以推断出该中间体具有配位不饱和的开放三角结构,该结构具有两个桥连的羰基,一个桥连分裂的(CO)4 Os(Os(CO)2(二烯)键。