Reactions of Doubly Bridged Bis(cyclopentadienes) with Iron Pentacarbonyl
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- 作者：Baiquan Wang ; Bolin Zhu ; Jianyong Zhang ; Shansheng Xu ; Xiuzhong Zhou ; and Linhong Weng
- 刊名：Organometallics
- 出版年：2003
- 出版时间：December 22, 2003
- 年：2003
- 卷：22
- 期：26
- 页码：5543 - 5555
- 全文大小：425K
- 年卷期：v.22,no.26(December 22, 2003)
- ISSN：1520-6041
文摘
When the doubly bridged bis(cyclopentadiene) ligand (Me2C)(Me2Si)(C5H4)2 (1) reacted withFe(CO)5 in refluxing toluene, the unusual product [(C5H6)(Me2C)(Me2Si)(
5-C5H3)Fe(CO)]2(
-CO)2 (2) with a hydrogenated double bond in one of the cyclopentadiene ligands, the diironcomplex (Me2C)(Me2Si)[(5-C5H3)Fe(CO)2]2 (3), and the desilylation product 4 were obtained.When the reaction was performed in refluxing xylene, the novel complex (Me2C)(5-C5H3)(5:1-C5H3)[(Me2Si)Fe(CO)2][Fe(CO)2] (5) with an Fe-Si bond, which should be accompaniedby the cleavage of a C-Si bond in the ligand, was isolated in addition to the complexes 2~4.When bis(cyclopentadienyl) ligands bridged with R2C (R2C = Me2C, (CH2)5C) and Me2E(E = Si, Ge) groups were used instead of 1, the similar novel complexes (R2C)(5-C5H3)(5:1-C5H3)[(Me2E)Fe(CO)2][Fe(CO)2] (R2C = Me2C, E = Ge (7); R2C = (CH2)5C, E = Si (17), Ge(21)) with an Fe-E bond were obtained in addition to the diiron complexes (R2C)(Me2E)[(5-C5H3)Fe(CO)]2(-CO)2 (R2C = Me2C, E = Ge (8); R2C = (CH2)5C, E = Si (18), Ge (22))and the desilylation or degermylation products. When a tert-butyl group was introducedinto the cyclopentadienyl rings, or two phenyl groups were introduced at the bridging siliconatom instead of two methyl groups in 1, only the diiron complexes (Me2C)(Me2E)[(5-t-BuC5H2)Fe(CO)2]2 (E = Si(10), Ge (13)) and (Me2C)(Ph2Si)[(5-C5H3)Fe(CO)2]2 (15) wereobtained, in addition to the desilylation or degermylation products. When a methylene bridgewas used instead of an isopropylene bridge in 1 and 6, the partially hydrogenated complexes(Me2E)(3-CHC5H6)(5-C5H3)Fe(CO)3Fe(CO)2 (E = Si (24), Ge (28)), the diiron complexes(CH2)(Me2E)[(5-C5H3)Fe(CO)]2(-CO)2 (E = Si (25), Ge (29)), and the desilylation ordegermylation products were obtained. The molecular structures of 2, 3, 5, 7, 8, 10, 11t, 15,17, 18, 21, 24, 25, 28, and 29 were determined by X-ray diffraction.
5-C5H3)Fe(CO)]2(-CO)2 (2) with a hydrogenated double bond in one of the cyclopentadiene ligands, the diironcomplex (Me2C)(Me2Si)[(5-C5H3)Fe(CO)2]2 (3), and the desilylation product 4 were obtained.When the reaction was performed in refluxing xylene, the novel complex (Me2C)(5-C5H3)(5:1-C5H3)[(Me2Si)Fe(CO)2][Fe(CO)2] (5) with an Fe-Si bond, which should be accompaniedby the cleavage of a C-Si bond in the ligand, was isolated in addition to the complexes 2~4.When bis(cyclopentadienyl) ligands bridged with R2C (R2C = Me2C, (CH2)5C) and Me2E(E = Si, Ge) groups were used instead of 1, the similar novel complexes (R2C)(5-C5H3)(5:1-C5H3)[(Me2E)Fe(CO)2][Fe(CO)2] (R2C = Me2C, E = Ge (7); R2C = (CH2)5C, E = Si (17), Ge(21)) with an Fe-E bond were obtained in addition to the diiron complexes (R2C)(Me2E)[(5-C5H3)Fe(CO)]2(-CO)2 (R2C = Me2C, E = Ge (8); R2C = (CH2)5C, E = Si (18), Ge (22))and the desilylation or degermylation products. When a tert-butyl group was introducedinto the cyclopentadienyl rings, or two phenyl groups were introduced at the bridging siliconatom instead of two methyl groups in 1, only the diiron complexes (Me2C)(Me2E)[(5-t-BuC5H2)Fe(CO)2]2 (E = Si(10), Ge (13)) and (Me2C)(Ph2Si)[(5-C5H3)Fe(CO)2]2 (15) wereobtained, in addition to the desilylation or degermylation products. When a methylene bridgewas used instead of an isopropylene bridge in 1 and 6, the partially hydrogenated complexes(Me2E)(3-CHC5H6)(5-C5H3)Fe(CO)3Fe(CO)2 (E = Si (24), Ge (28)), the diiron complexes(CH2)(Me2E)[(5-C5H3)Fe(CO)]2(-CO)2 (E = Si (25), Ge (29)), and the desilylation ordegermylation products were obtained. The molecular structures of 2, 3, 5, 7, 8, 10, 11t, 15,17, 18, 21, 24, 25, 28, and 29 were determined by X-ray diffraction.