摘要
首次对 Co2 ( CO) 8和有机膦配体〔PPh3 、P( OPh) 3 〕的固相合成反应进行了研究 .对产物做了元素分析 ,IR、1HNMR、3 1PNMR、MS等波谱表征 ,并对产物的立体结构和反应机理进行推测 .产物〔cis-Co( CO) 3 ( PPh3 ) 2 〕+ 〔Co( CO) 4〕-中的阳离子结构对称性为 Cs,不同于液相条件下反应产物的阳离子结构对称性 D3 h.这种结构的差异导致 P原子所受的反位影响不同 ,因而固相和液相反应产物的 3 1PNMR化学位移 δ值不同 .产物〔Co( CO) 3 P( OPh) 3 〕2 的对称性为D3 d,与液相反应产物立体结构相同 ,但反机理不同 .反应物 Co2 ( CO) 8在固态和在溶液中的结构差异 ,Co-Co键在反应中断裂与否以及 CO的流变性是影响产物结构的主要因素 .
This Thesis firstly made some researchs on the reactions of Co 2(CO) 8 with organic phosphine ligands PPh 3 and P(OPh) 3 in the solid state .The products 〔cis-Co(CO) 3(PPh 3) 2〕+〔Co(CO) 4〕- and 〔Co(CO) 3P(OPh) 3〕 2 were characterized by the elementary analysis ,IR, 31 PNMR, 1 HNMR and MS spectroscopy. The structure of two products and mechanism of the reactions were infered. The symmetiy Cs of〔 cis-Co(CO) 3(PPh 3)〕+ which was obtained in the solid state reaction was different to the symmetry D 3h of 〔trans-Co(CO) 3(PPh 3) 2〕+ which was obtained in the liguid state reaction. The distinction of two structares led to the different influence on the atom P and different δ 31 P. The dinuclear product 〔Co(CO) 3P(OPh 3)〕 2 which was obtained in the solid state reaction had the same structare with the product in the liquid state reaction, i.e., D 3d , but the reaction mechanisms were different. We infered that distinction of structures of Co 2(CO) 8 in solid state and liquid state, breaking of Co-Co bond and fluxtionality of CO in the reactions were main reasons for influence structure of the products.
出处
《内蒙古大学学报（自然科学版）》
CAS
CSCD
2000年第4期402-405,共4页
Journal of Inner Mongolia University：Natural Science Edition
基金
国家自然科学基金资助项目!(29861001)
关键词
八羰基二钴
有机膦
固相反应
配体
Octacarbonyldicobalt
organic phosphine
solid state reaction
