含半填隙磷原子配体六核钴羰合簇的P(OEt)_3和PPh_3取代衍生物的合成和表征

用 P( OEt) 3和 PPh3分别与 Co6(μ6-P) (μ,η2 -SCH2 CH2 CH2 S) (μ-PSCH2 CH2 CH2 S)( CO) 12 进行取代反应 ,首次得到 4个一取代和 1个二取代含半填隙磷原子配体六核钴羰基簇合物的取代衍生物 ,化学式如下 :Co6( μ6-P) ( μ,η2 -SCH2 CH2 CH2 S) ( μ-PSCH2 CH2 CH2 S)( CO) 11〔P( OEt) 3〕 ( a 和 b,同分异构体 ) ,Co6( μ6-P) ( μ,η2 -SCH2 CH2 CH2 S) ( μ-PSCH2 CH2 CH2 S) (μ-CO) ( CO) 9〔P( OEt) 3〕2 ( ) ,Co6(μ6-P) (μ,η2 -SCH2 CH2 CH2 S) (μ-PSCH2 CH2 CH2 S) ( CO) 11( PPh3) ( a) ,Co6( μ6-P) ( μ,η2 -SCH2 CH2 CH2 S) ( μ-PSCH2 CH2 CH2 S) ( μ-CO) ( CO) 10 ( PPh3) ( b) .对 5个合成的簇合衍生物通过元素分析 ,IR( νco)、1HNMR、31PNMR和 MS谱学表征 ,发现 a和 b, a和 b 是一取代的同分异构体 ,P( OEt) 3和 PPh3可能取代母体钴簇合物基底不同钴原子上的一个 CO. 是二取代产物 ,两个P( OEt) 3分子可能各取代母体钴簇合物在顶端的两个钴原子上的一个 CO.

Syntheses and Characterization of Substituted Derivatives of Co_6 Carbonyl Cluster Containing a Semi-interstitial P Atom with P(OEt)_3 and PPh_3

The reaction of P(OEt)3/PPh3 with Co6(μ6-P)(μ,η2-SCH2CH2CH2S)(μ-)(CO)12 yields four monosubstituted and one disubstituted new Co6 carbonyl cluster derivatives containing a semi-interstitial P Atom as follows:Co6(μ6-P)(μ,η2-SCH2CH2CH2S)(μ- )(CO)11〔P(OEt)3〕 (Ⅰa和Ⅰb，isomers),Co6(μ6-P)(μ,η2-SCH2CH2CH2S)(μ- )(μ-CO)(CO)9〔P(OEt)3〕2 (Ⅱ),Co6(μ6-P)(μ,η2-SCH2CH2CH2S)(μ- )(CO)11(PPh3) (Ⅲa) and Co6(μ6-P)(μ,η2-SCH2CH2CH2S)(μ-)(μ-CO)(CO)10(PPh3) (Ⅲb). These cluster derivatives were characterized by elementary analysis, IR(co)、1 HNMR、31 PNMR and MS spectroscopy respectiuely. lt were shown that Ⅰa and Ⅰb, Ⅲa and Ⅲb are the monosubstituted isomers. In the reaction, the phosphite/phosphinc ligands may be substituted in the matrix Co6 cluster for one CO either at the basal Co atom which possesses with two CO or at the another basal Co atom which possesses with one CO. The Ⅱ are a disubstituted derivative and two phosphite ligands may be substituted for each of the CO at the apical two Co atoms of the matrix Co6 cluster.