Experimental and DFT Study of the Tautomeric Behavior of Cobalt-Containing Secondary Phosphine Oxides
作者:Chu-Hung Wei、Cheng-En Wu、Yi-Luen Huang、Roman G. Kultyshev、Fung-E. Hong
DOI:10.1002/chem.200601051
日期:2007.2.2
New cobalt-containing secondary phosphine oxides [(mu-PPh(2)CH(2)PPh(2))Co(2)(CO)(4)mu,eta-PhC[triple chemical bond]CP(==O)(H)(R)}] (8 a: R=tBu; 8 b: R=Ph) were prepared by reaction of secondary phosphine oxides PhC[triple chemical bond]CP- (==O)(H)(R) (6 a: R=tBu; 6 b: R=Ph) with dppm-bridged dicobalt complex [(mu-PPh(2)CH(2)PPh(2))Co(2)(CO)(6)] (2). The molecular structures of 8 a and 8 b were determined
新的含钴仲膦氧化物[(mu-PPh(2)CH(2)PPh(2))Co(2)(CO)(4)mu,eta-PhC [三化学键] CP(== O )(H)(R)}](8 a:R = tBu; 8 b:R = Ph)通过仲膦氧化物PhC [三化学键] CP-(== O)(H)(R )(6 a:R = tBu; 6 b:R = Ph),带有dppm桥联的二钴络合物[[mu-PPh(2)CH(2)PPh(2))Co(2)(CO)(6)] (2)。通过单晶X射线衍射确定8a和8b的分子结构。尽管使用8b作为配体的钯催化的Heck反应获得令人满意的结果,但是8a在相同反应中的表现较差。从这些结果来看,8 b及其异构形式[[mu-PPh(2)CH(2)PPh(2))Co(2)(CO)(4)mu,eta-PhC [三元组]化学键] CP(OH)(Ph)}] 8 b'确实发生了,但在8 a和[(mu-PPh