硅烷基五羰基锰（ＣＯ）５ＳｉＲ３的光化学合成

摘要 对甲基卞基五羰基锰(CO)5Mn-p-CH2C6H4CH3（4a）或对甲氧基五羰基锰(CO)5Mn-p-CH2C6H4OCH3（4b）与1-2当量R3SiH的C6H6 或C6D6溶液在5oC光解，经色谱纯化后得到中等或高收率硅烷基五羰基锰(CO)5MnSiR3［SiR3 = SiMe2Ph（１b），SiMePh2（１c），SiPh3（１d），SiHPh2（１e），SiEt3（１f），SiMe2tBu（１g），和SiMe2Et（１h）］。光化学反应后，对二甲苯和对甲基苯甲醚副产物分别定量生成，并伴随少量Mn2(CO)10（<1％-6％）。色谱柱的尺寸和温度（室温至- 65 oC）的选择视初始浓度的分解，色谱柱展开期间1的稳定性（过载），以及1与Mn2(CO)10的分离难易而定。去除Mn2(CO)10后的硅烷基五羰基锰3b-3g为浅黄色油状物或无色晶体（只有3h无法分离得到纯净物）。尽管这些化合物对空气敏感对热却相对稳定。

Photochemical Syntheses of Silyl Manganese Pentacarbonyls (CO)5SiR3

Abstract Photolysis of paramethyl benzyl manganese pentacarbonyl (CO)5Mn-p-CH2C6H4CH3 (4a)and paramethoxy benzyl manganese pentacarbonyl (CO)5Mn-p-CH2C6H4OCH3(4b) with 1-2 equivalents of R3SiH in C6H6 or C6D6 at 5℃ yields the silyl manganese pentacarbonyls (CO)5MnSiR3 SiR3 = SiMe2Ph (1b), SiMePh2 (1c), SiPh3 (1d), SiHPh2 (1e), SiEt3 (1f), SiMe2tBu(1g), and SiMe2Et (1h) ] in moderate to high yields after chromatographic purification. Quantitative production of respective byproducts p-xylene and p-methylanisole, along with variable yields of Mn2(CO)10 (<1 % to 6 %) are observed after the photochemical reaction. Conditions for the chromatographic isolation differ for each product. Choice of column size and temperature (room temperature to - 65 ℃) is made according to initial concentration-dependent decomposition (overloading), stability during development and separability of 1 with Mn2(CO)10. Once freed from Mn2(CO)10 1b - 1g were isolated as pale yellow oil or off white crystals (only 3h was not isolated pure). Although very air sensitive these products are otherwise stable thermally.