Divergent Isomerization Behavior and Rhodium(I) Coordination Chemistry of Indenyl Ligands Bearing either One or Two Pnictogen Donor Fragments
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- 作者：Judy Cipot ; Dominik Wechsler ; Mark Stradiotto ; Robert McDonald ; and Michael J. Ferguson
- 刊名：Organometallics
- 出版年：2003
- 出版时间：December 8, 2003
- 年：2003
- 卷：22
- 期：25
- 页码：5185 - 5192
- 全文大小：187K
- 年卷期：v.22,no.25(December 8, 2003)
- ISSN：1520-6041
文摘
1-(Diphenylphosphino)-2-(dimethylamino)indene (2c) has been prepared in 61% yield andupon exposure to Al2O3 is mostly isomerized to 3-(diphenylphosphino)-2-(dimethylamino)indene (2d) (2c:2d 
1:3); similarly, 1-(diisopropylphosphino)-2-(dimethylamino)indene (2a)is only partially converted to the corresponding C3 isomer (2b) upon treatment with Al2O3(2a:2b 3:1). In contrast, 1-(diisopropylphosphino)indene (6a) has been prepared in 92%yield and is easily converted to 3-(diisopropylphosphino)indene (6b) on passing over Al2O3;0.5 equiv of [(
4-COD)RhCl]2 and 6b combine to give [(
1-P-6b)(4-COD)RhCl] (7) in 79%yield. Treatment of either 2-(dimethylamino)indene (1) or 6b with a stoichiometric amountof n-BuLi, followed by the addition of 0.5 equiv of [(4-COD)RhCl]2, produces the (5-indenyl)rhodium(I) complexes 8 (53% yield) and 9 (88% yield), respectively, in which the pnictogendonor is apparently not coordinated to the rhodium center. When 2.5 equiv of n-BuLi iscombined with 6b and subsequently treated with 0.5 equiv of [(4-COD)RhCl]2, 9 is alsoproduced, along with a small amount of the unusual Rh2Li2 species 10. The crystallographically determined structures of 2d, 3·C6H6, 7, and 10·C7H8 are reported.
1:3); similarly, 1-(diisopropylphosphino)-2-(dimethylamino)indene (2a)is only partially converted to the corresponding C3 isomer (2b) upon treatment with Al2O3(2a:2b 3:1). In contrast, 1-(diisopropylphosphino)indene (6a) has been prepared in 92%yield and is easily converted to 3-(diisopropylphosphino)indene (6b) on passing over Al2O3;0.5 equiv of [(4-COD)RhCl]2 and 6b combine to give [(1-P-6b)(4-COD)RhCl] (7) in 79%yield. Treatment of either 2-(dimethylamino)indene (1) or 6b with a stoichiometric amountof n-BuLi, followed by the addition of 0.5 equiv of [(4-COD)RhCl]2, produces the (5-indenyl)rhodium(I) complexes 8 (53% yield) and 9 (88% yield), respectively, in which the pnictogendonor is apparently not coordinated to the rhodium center. When 2.5 equiv of n-BuLi iscombined with 6b and subsequently treated with 0.5 equiv of [(4-COD)RhCl]2, 9 is alsoproduced, along with a small amount of the unusual Rh2Li2 species 10. The crystallographically determined structures of 2d, 3·C6H6, 7, and 10·C7H8 are reported.