The photochemistry of [M
3
(CO)
12
]
(M = Ru 1a or Os 1b) with nitrogen heterocycles has been
studied. In all cases photolysis leads to photosubstitution products,
the heterocycles inhibiting the photofragmentation pathway. With
pyridine (py) 1a formed the orthometallated complex
[Ru
3
H(CO)
10
(C
5
H
4
N)] 2a. With
osmium, the simple substitution product
[Os
3
(CO)
11
(py)] 3b can be isolated. With
2-methylpyridine (mpy)
[Ru
3
H(CO)
10
(2-MeC
5
H
3
N)] 5a
and [Os
3
(CO)
11
(mpy)] 6b were formed from 1a and 1b
respectively. With 2,6-dimethylpyridine no net photoreaction was
observed. Photolysis of 1a and 1b with 2,2′-bipyridine led to the
formation of [M
3
(CO)
10
(bipy)]
(M = Ru 7a and Os 7b). The molecular structure of 7b has
been obtained by single-crystal X-ray diffraction studies. Photolysis of
1a and 1b with pyridazine (pydz) led to the substituted products
[M
3
(CO)
10
(pydz)] (M = Ru 8a or Os
8b).
研究了[M 3 (CO) 12 ](M = Ru 1a 或 Os 1b)与氮杂环的光
化学作用。在所有情况下,光解都会导致光置换产物,杂环会抑制光破碎途径。1a 与
吡啶 (py) 形成正
金属化复合物 [Ru 3 H(CO) 10 (C 5 H 4 N)] 2a。用
锇可以分离出简单的取代产物[Os 3 (CO) 11 (py)]3b。用 2-
甲基吡啶(mby)分别从 1a 和 1b 生成 [Ru 3 H(CO) 10 (2-MeC 5 H 3 N)] 5a 和 [Os 3 (CO) 11 (mpy)] 6b。在 2,6-二
甲基吡啶中没有观察到净光反应。1a 和 1b 与 2,2′-联
吡啶光解后生成 [M 3 (CO) 10 (bipy)](M = Ru 7a 和 Os 7b)。通过单晶 X 射线衍射研究获得了 7b 的分子结构。1a 和 1b 与
哒嗪(pydz)发生光解反应,生成取代产物 [M 3 (CO) 10 (pydz)](M = Ru 8a 或 Os 8b)。