Synthesis,Structure and Reaction of Metal-Metal Bonded Binuclear Cr-Cr and Heterobimetallic Fe-Cr Phosphido-Bridged complex
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 afford...
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| Other Authors: | |
| Format: | Others |
| Language: | zh-TW |
| Published: |
1995
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| Online Access: | http://ndltd.ncl.edu.tw/handle/05764047164210069080 |
| Summary: | 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
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