Perchlorate and difluorophosphate coordination derivatives of manganese carbonyl
Perchlorate and difluorophosphate coordination derivatives of manganese carbonyl
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羰基锰的高氯酸盐和二氟磷酸盐配位衍生物
DOI：
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发表时间：
1978
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通讯作者：
F. Wimmer
中科院分区：
文献类型：
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作者：
F. Wimmer
配合物Mn（CO）_5（OClO_3）和Mn（CO）_3L_2（OClO_3）（L = PPh_3，P（OPh）_3; L_2 = bpy ~*）是由相应的溴代配合物在二氯甲烷中与AgClO_4发生萃取反应生成的。高氯酸根络合物已通过红外光谱表征。和质谱。它们经历容易的取代反应，其中高氯酸根基团被卤离子（X- = Cl、Br、I）、膦[PR 3（R = Ph、对甲苯基、间甲苯基）、dpe、dpm]* 或溶剂分子（MeCN、PhCN、MeOH、Me 2CO、py*）取代。与氟离子反应产生Mn（CO）3F 3和其他分解产物。当Mn（CO）5X和Mn（CO）3L 2X（X = Br）与AgPF 6在二氯甲烷中反应时，PF 6-离子发生水解，产生相应的二氟磷酸根络合物（X = PO 2F 2-），其已通过i.r.，19F N.M.R.和质谱。它们在低温下相当稳定，但在室温下分解。二氟磷酸根基团比高氯酸根基团更惰性，取代率按CO = PPh 3> bpy > P（OPh）3的顺序降低。
The complexes Mn(CO)5(OClO3) and Mn(CO)3L2(OClO3) (L = PPh3, P(OPh)3; L2 = bpy*) are formed by abstraction reactions with AgClO4 from the corresponding bromo complexes in dichloromethane. The perchlorato complexes have been characterized by i.r. and mass spectroscopy. They undergo facile substitution reactions in which the perchlorato group is replaced by halide ions (X- = Cl, Br, I), phosphines [PR3 (R = Ph, p- tolyl, m-tolyl), dpe, dpm]* or solvent molecules (MeCN, PhCN, MeOH, Me2CO, py*). Reaction with fluoride ion yields Mn(CO)3F3 plus other decomposition products. When Mn(CO)5X and Mn(CO)3L2X (X = Br) are made to react with AgPF6 in dichloromethane, hydrolysis of the PF6- ion occurs to yield the corresponding difluorophosphato complexes (X = PO2F2-), which have been characterized by i.r., 19F N.M.R. and mass spectroscopy. They are reasonably stable at low temperatures, but decompose at room temperature. The difluorophosphato group is more inert than perchlorato with the rate of substitution decreasing in the order CO ≈ PPh3 > bpy > P(OPh)3.