Perparation, spectra and crystal structures of some Bis(cyclopentadienyl)ethylene or Bis(cyclopentadienyl)butadiene bridged homodinuclear or hettetrodinnuclear compplexes

• Main Author: 林奇邦
• Other Authors: 王玉蘋
• Format: Others
• Language: zh-TW
• Published: 1998
• Online Access: http://ndltd.ncl.edu.tw/handle/30402549350816061258

碩士 === 東海大學 === 應用化學研究所 === 86 === 　　Through Wittig reactions, compounds (η5-C5H5)Fe(η5-C5H4)-CH=CH-CN (29:E ; 30:Z) were made in 51% and 12% yield, respectively, from compound (η5-C5H5)Fe(η5-C5H4)-CHO 23 with ylide NCCH2P+Ph3C1-, and compound 29 was treated with DIBAL-H for reduction to give (η5-C5H5)Fe(η5-C5H4)-CH=CH-CHO (31:E) in 79% yield. 　　Through Wittig reactions, compounds (CO)2(NO)Cr(η5-C5H4)-CH=CH-CHO (32:E), and (CO)3(CH3)W(η5-C5H4)-CH=CH-CHO (33:E) were made in 26% and 23% yeild, respectively, from compounds (CO)2(NO)Cr(η5-C5H4)-CHO 20 and (CO)3(CH3)W (η5-C5H4)-CHO 25 with ylide OHCCH2P+Ph3C1- and weak base K2CO3, respectively. 　　Through Wittig reactions, compounds (η5-C5H5)Fe(η5-C5H4)-CH=CH-CH=CH-(η5-C5H4)Fe (η5-C5H5) (38:E,E), and (CO)2(NO)Cr(η5-C5H4)-CH=CH-CH--(η5-C5H4)Fe (η5-C5H5) (39:E,E ; 40:E,Z), and(CO)3(CH3)W (η5-C5H4)-CH=CH-CH=CH-(η5-C5H4)Fe (η5-C5H5)(41:E,E ; 42:E,Z) were made in 41%and 65%and 51% yeild, respectively, from compounds 31、32、33 with ylide(η5-C5H5)Fe(η5-C5H4)-CH2P+Ph3I-37, respectively. 　　Through Wittig reactions, compounds(η5-C5H5)Fe(η5-C5H4)-CH=CH-CH=CH-C6H5(43:E,E ; 44:Z,E), and (CO)2(NO)Cr(η5-C5H4)-CH=CH-CH=CH-C6H5(45:E,E ; 46:Z,E), and(CO)3(CH3)W (η5-C5H4)-CH=CH-CH=CH-C6H5(47:E,E ; 48:Z,E), and (η5-C5H5)Fe(η5-C5H4)-CH=CH-C6H5(49:E ; 50:Z) were made in 68% and 66% and 73% and 81% yeild, respectively, from compounds 20、23、25 with ylide C6H5-CH=CH-CH2P+Ph3C1- and C6H5CH2P+h3I-, respectively. 　　Compound 23 was treated with LDA and dropped slowly with CH3COCH3 for Aldol condensation in THF solution to give(η5-C5H5)Fe(η5-C5H4)-CH=CH-COCH3(58:E) and(η5-C5H5)Fe(η5-C5H4)-CH=CH-CO-CH=CH-(η5-C5H4)Fe (η5-C5H5)(59: E,E) in 48% and 11% yield, respectively. Compoud 58 was treated with Fe2(CO)9 to give η4-1,3-diene-Fe(CO)3 complex 60 in 21% yield. All compounds were characterized with 1H, 13C-NMR, IR, Mass spectra and elemental analysis. The assignments of C(2,5) and C(3,4) of cyclopentadiene ring moiety were based on their 2D-1H, 13C-HetCOR NMR spectra. 　　The structures of 29、30、31、32、33、45、53、55、57、58 and 60 had been solved by X-ray diffraction studies. Crystallographic data for 29: space group P21, monoclinic, a=6.395(16)A(angstron), b=7.596(3)Ac=12.233(20)A,β 101.684(17)° , Z=2. Crystallographic data for 30: space group P21/c, monoclinic, a=10.417(22)A(angstron), b=7.567(15)A, c=26.707(7)A, β99.344(21)° , Z=8. Crystallographic data for 31: space group P212121, a=7.935(19)A(angstron), b=11.130(3) A, c=12.489(3)A,Z=4. Crystallographic data for 32: space group P□ , triclinic, a=6.776(3) A(angstron), b=7.488(6)A, c=11.466(6)A, α 107.289(6)°, β93.967(4)°,γ92.644(6)°,Z=2. Crystallographic data for 33: space group P21/c, monoclinic, a=10.714(3)A(angstron), b=8.453(14)A, c=14.916(3)A, β107.357(24)°, Z=4. Crystallographic data for 45: spzce group P21, monoclinic, a=6.189(13)A(angstron), b=7.617(14)A, c=16.410(4)A, β92.591(19)°, Z=2. Crystallographic data for 53: spzce group P21/c, monoclinic, a=11.000(3)A(angstron), b=11.785(14)A, c=12.629(3)A, β104.729(22)°, Z=4. Crystallographic data for 55: space group P21/c, monoclinic, a=11.800(21)A(angstron), b=12.383(3)A, c=11.428(16)A, β111.671(13)°, Z=4. Crystallographic data. for 57: space group P21/n, monoclinic, a=7.815(20)A(angstron), b=13.064(5)A, c=11.084(3)A,β91.732(21)°, Z=4. Crystallographic data for 58: space group P21/c, monoclinic, a=14.835(3) A(angstron), b=5.856(10)A, c=13.281(21)A,β96.900(15)°, Z=4. Crystallographic data for 60: space group P , triclinic, a=7.774(13)A(angstron), b=10.121(20)A, c=10.359(21)A, α95.698(17)°, β92.916(15)°, γ102.545(15)°, Z=2.