107(6) kJ mol-1 were derived from an Eyring plot. The analogous cluster complex 3b with μ-P(i-Bu)2 bridges has been obtained, too. Its structure has been confirmed by single-crystal X-ray analysis. 2a and 2b are highly photosensitive in solution. Upon exposure to daylight, they rearrange to give the novel wheel-shaped cluster complexes Os6(μ6-Hg)(μ-PR2)2(CO)20 (R = Ph 4a, i-Bu 4b). The structure of 4a
的反应[P
PN] [O的3(μ-PR 2)(CO)10 ](R =苯基1a中,我-Bu 1B)与升
汞2在THF中在光照下的排斥-90℃,得到螺环簇μ 4 -Hg [O的3(μ-PR 2)(μ-CO)(CO)9 ] 2(R =苯基2a中,我-Bu 2B)。在这些化合物中μ 4 -Hg桥接每个OS中的一个OS-O的边缘3亚基。剩余的四个边缘由μ-CO和μ-PPH桥接2个
配体分别。13在室温下记录的13个富含CO的2a的C NMR光谱表明,OS 3亚基绕着穿过
汞原子的轴及其桥接的OS-OS矢量的中点进行了分子内旋转。当2a在
甲苯或1,4-
二恶烷中加热时,
金属骨架发生重排。该μ 4 -Hg部分被移位到该OS中的一个的另一边缘3环,得到异构体(CO)10(μ-PPH 2)
锇3(μ 4 -Hg)O的3(μ-PPH 2)(μ -CO)(CO)9,图3a。该过程的动力学通过分别在
甲苯和1,4-
二恶烷中的四个不同温度下的UV