Asymmetric Induction and Configurational Stability at the Metal Center in Half-Sandwich (6-p-Cymene)ruthenium(II) an
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- 作者：Dario Drommi ; Felice Faraone ; Giancarlo Franciò ; Daniele Belletti ; Claudia Graiff ; and Antonio Tiripicchio
- 刊名：Organometallics
- 出版年：2002
- 出版时间：February 18, 2002
- 年：2002
- 卷：21
- 期：4
- 页码：761 - 764
- 全文大小：63K
- 年卷期：v.21,no.4(February 18, 2002)
- ISSN：1520-6041
文摘
The reactions of the complexes [Ru(
6-p-cymene)Cl2]2 and [Rh(5-C5Me5)Cl2]2 with the ligandsPhosphito-N ((S)-8-((3,5-dioxa-4-phosphacyclohepta[2,1-a;3,4-a']dinaphthalen-4-yl)oxy)quinoline, (S)-1) and Phosphonito-N ((R)-8-(3,5-dioxa-4-phosphacyclohepta[2,1-a;3,4-a']dinaphthalen-4-yl)quinoline, (R)-2) were investigated. The reactions of (S)-1 with [Ru(6-p-cymene)Cl2]2and [Rh(5-C5Me5)Cl2]2 give the complexes [Ru(6-p-cymene)(S-1)Cl2] (3) and [Rh(5-C5Me5)(S-1)Cl2] (5).Treatment of 3 and 5 with NH4PF6 promoted thechelation process of the P-coordinated ligand (S)-1,affording the corresponding chelate complexes [Ru(6-p-cymene)(S-1)Cl]PF6 (4) and [Rh(5-C5Me5)(S-1)Cl]PF6(6) with high stereoselectivity. The absolute configurationof the major diastereoisomer 6a was determined by X-raydiffractometry. The reaction of (R)-2 with [Ru(6-p-cymene)Cl2]2 and [Rh(5-C5Me5)Cl2]2 afforded in one potthe chelate complexes [Ru(6-p-cymene)(R-2)Cl]Cl (7) and[Rh(5-C5Me5)(R-2)Cl]Cl (8); the latter was obtained asthe only diastereoisomer. The asymmetric induction andthe configurational stability at the metal center of thecationic half-sandwich ruthenium and rhodium diastereoisomers are considered.
6-p-cymene)Cl2]2 and [Rh(5-C5Me5)Cl2]2 with the ligandsPhosphito-N ((S)-8-((3,5-dioxa-4-phosphacyclohepta[2,1-a;3,4-a']dinaphthalen-4-yl)oxy)quinoline, (S)-1) and Phosphonito-N ((R)-8-(3,5-dioxa-4-phosphacyclohepta[2,1-a;3,4-a']dinaphthalen-4-yl)quinoline, (R)-2) were investigated. The reactions of (S)-1 with [Ru(6-p-cymene)Cl2]2and [Rh(5-C5Me5)Cl2]2 give the complexes [Ru(6-p-cymene)(S-1)Cl2] (3) and [Rh(5-C5Me5)(S-1)Cl2] (5).Treatment of 3 and 5 with NH4PF6 promoted thechelation process of the P-coordinated ligand (S)-1,affording the corresponding chelate complexes [Ru(6-p-cymene)(S-1)Cl]PF6 (4) and [Rh(5-C5Me5)(S-1)Cl]PF6(6) with high stereoselectivity. The absolute configurationof the major diastereoisomer 6a was determined by X-raydiffractometry. The reaction of (R)-2 with [Ru(6-p-cymene)Cl2]2 and [Rh(5-C5Me5)Cl2]2 afforded in one potthe chelate complexes [Ru(6-p-cymene)(R-2)Cl]Cl (7) and[Rh(5-C5Me5)(R-2)Cl]Cl (8); the latter was obtained asthe only diastereoisomer. The asymmetric induction andthe configurational stability at the metal center of thecationic half-sandwich ruthenium and rhodium diastereoisomers are considered.