| Summary: | 碩士 === 東海大學 === 化學系 === 88 === There are two sections in this thesis. The first section is the preparation of the derivatives of (η5-C5H5)Cr(CO)2NO 8, by replacing the metal coordi- nated ligands. Compounds are [η5-(C5H4-COOCH3)]Cr(NO)2Br 40, [η5- (C5H4-COOH)]Cr(NO)2Br 41, [η5-(C5H4-COOCH3)]Cr(NO)2NCSe 42, [η5- (C5H4-COOCH3)]Cr(NO)2NCS 43 and [η5-(C5H4-CO-Ph)]Cr(NO)2Br 44. Changing the ligand from CH3 to CN, compound [η5-(C5H4-COOCH3)]W- (CO)3CN 45 was prepared, a derivative of (η5-C5H5)W(CO)3CH3 28. Com- pounds 40 (84%), 41 (78%) and 44 (86%) were obtained from the corres- ponding compounds 22, 24, and 23, respectively via bromination/ nitro- sylation.
Compound 42 (46%) was obtained from the chloride compound 36 after first treating with AgNO3 and subsequently with KSeCN. Analogously, sub- sequently treating with to KSCN, 43 (52%) was obtained. The same pro- cedure was followed for the formation of compound 45 (28%) from 32. It is worthwhile to mention that compound 45 could also be prepared from com- pound 29, after treating with ClSiMe3 and KCN. All compounds listed were characterized with 1H, 13C-NMR, IR, mass spectra and elemental analysis. The assignment of C(2,5) and C(3,4) of cyclopentadiene ring moiety were based on their 2D-1H, 13C-HetCOR NMR spectra.
The second section deals with some σ-acetylide organometallic com- plexes. A dinuclear acetylenebridged coupling was led when 2 equivalents of [η5-(C5H4-COOCH3)]W(CO)3I 33 reacted with (n-Bu)3SnC≣CSn(n-Bu)3. Compound [η5-(C5H4-COOCH3)]W(CO)3C≣C(CO)3W[η5-(C5H4-COOCH3)] 47 was obtained. The same symmetric compounds [η5-(C5H4-COOCH3)]Cr- (NO)2C≣C(NO)2Cr[η5-(C5H4-COOCH3)] 48 and (η5-C5H5)Mo(CO)3C≣C- (CO)3Mo(η5-C5H5) 49 were prepared from analogous procedures. When compound (η5-C5H5)Fe[η5-(C5H4-C≣CH)] 26 was treated with Et2Sn- (n-Bu)3, (η5-C5H5)Fe(η5-C5H4)-C≣CSn(n-Bu)3 27 was obtained. Sub- sequently 27 was reacted with [η5-(C5H4-COOCH3)]W(CO)3I 33, via palla- dium-catalyzed coupling, led to (η5-C5H5)Fe(η5-C5H4)-C≣C-(CO)3W[η5- (C5H4-COOCH3)] 50 (49%), a heterodinuclear complex. Complexes (η5- C5H5)Fe(η5-C5H4)-C≣C-(NO)2Cr[η5-(C5H4-COOCH3)] 51 (49%) and (η5- C5H5)Fe(η5-C5H4)-C≣C-(CO)3W(η5-C5H5) 52 (46%) were obtained by following the similar procedures. When compounds [η5-(C5H4-COOCH3)]- W(CO)3Cl 32, (η5-C5H5)Cr(NO)2Cl 35 and [η5-(C5H4-COOCH3)]Cr(NO)2Cl 36 were reacted with HC≣C-Ph respectively, in the presence of CuI catalyst, compounds [η5-(C5H4-COOCH3)]W(CO)3(C≣C-Ph) 46 (75%), (η5-C5H5)- Cr(NO)2(C≣C-Ph) 38 (42%) and[η5-(C5H4-COOCH3)]Cr(NO)2(C≣C-Ph) 39 (38%) were obtained. The compounds of this section were also characterized with 1H, 13C-NMR, IR, mass spectra and elemental analysis. The assignment of C (2,5) and C(3,4) of cyclopentadiene ring moiety were based on their 2D-1H, 13C-HetCOR NMR spectra.
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