Synthesis,Structure and Reaction of Metal-Metal Bonded Binuclear Cr-Cr and Heterobimetallic Fe-Cr Phosphido-Bridged complex

• Main Authors: Liu,Fu-Tzu, 劉福賜
• Other Authors: Twu Jen
• Format: Others
• Language: zh-TW
• Published: 1995
• Online Access: http://ndltd.ncl.edu.tw/handle/05764047164210069080

碩士 === 文化大學 === 應用化學系 === 83 === 1. The metal-metal bonded phosphido-bridged binuclear complex (CO)4Cr(μ-PPh2)2Cr(CO)4 (10)， was prepared by the reactionof Li[Cr(CO)5(PPh2)] under reflux condition。Reduction of 10 with 1eq. of LiBEt3H affords isomers and with 2eq. of KB(sec-Bu)3H at 0oC generates [(CO)4Cr(μ-PPh2)2Cr(CO)4]2- (12) Reaction between 10 and RLi ( R = Me、 Ph ) yields [(CO)3(COR)Cr(μ- PPh2)2Cr(CO)4]- ( 13a；13b ) 2. The metal-metal bonded phosphido-bridged heterobimetallic complex (CO)3Fe(μ-PPh2)2Cr( CO)4 (11)， was prepared by the reaction of Li2[Cr(CO)4(PPh2)2] with Fe(CO)4Br2 Reduction of 11 with 1eq. of LiBEt3H affords [( CO)3(H)Fe(μ-PPh2)2Cr(CO)4]- (14)，Deprotonation of 14 with excess n-BuLi or LiBEt3H and KB(sec-Bu)3H generates [(CO)3Fe(μ- PPh2)2W(CO)4]2- (15)， which can also be obtained by the reduction of 11 with 2eq. of KB(sec-Bu)3H Protonation of 14 with excess CH3COOH gives Fe(CO)3(PPh2H) Protonation of 15 with H2O at -108oC affords 14 and [(CO)2(H)Fe(μ-PPh2)2Cr(CO)4]- (15a) under reflux condition Reaction between 11 and RLi ( R = Me、Ph ) yields [(CO)2(COR)Fe(μ-PPh2)2Cr(CO)4]- ( 16a；16b ). Alkylation of 15 with MeI in THF affords 16a as indicated by the 31P NMR spectra of the reaction solutions。Substitution of 11 with PPhMe2 gives (CO)2(PPhMe2)Fe(μ-PPh2)2Cr(CO)4 (11a) These structures of 10、11 and 11a were characterized by a complete single crystal X-ray diffraction study