Cage Substitution Reactions of Monocarbollide Carbonyl Complexes of Iron: Generation of Iminium Groups at a Boron Vertex
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- 作者：Andreas Franken ; Shaowu Du ; Paul A. Jelliss ; Jason A. Kautz ; and F. Gordon A. Stone
- 刊名：Organometallics
- 出版年：2001
- 出版时间：April 16, 2001
- 年：2001
- 卷：20
- 期：8
- 页码：1597 - 1607
- 全文大小：166K
- 年卷期：v.20,no.8(April 16, 2001)
- ISSN：1520-6041
文摘
Treatment of [N(PPh3)2][Fe(CO)2(L)(
5-7-CB10H11)] (L = SMe2, PPh3) in SMe2 or O(CH2)4with H2SO4 yields the neutral charge-compensated complexes [Fe(CO)2(L)(5-9-L'-7-CB10H10)](L = SMe2, L' = SMe2 (2), O(CH2)4 (3); L = PPh3, L' = SMe2 (4), O(CH2)4 (5)). An X-raycrystallographic study of 2 established that one of the exopolyhedral SMe2 groups is bondedto a boron in a 
-site with respect to the carbon in the CBBB B
CH gives [N(PPh3)2][Fe(CO)3(2:5-8-{(E)-C(H)=C(H)But}-7-CB10H10)] (14), which with NCMe in CF3SO3Me affords [Fe(CO)2(2:5-8-{(E)-C(H)=C(H)But}-10-{(E)-N(Me)=C(H)Me}-7-CB10H9)] (16). The site ofattachment of the exopolyhedral iminium and tert-butylvinyl substituents to the cage wasestablished by X-ray diffraction.
5-7-CB10H11)] (L = SMe2, PPh3) in SMe2 or O(CH2)4with H2SO4 yields the neutral charge-compensated complexes [Fe(CO)2(L)(5-9-L'-7-CB10H10)](L = SMe2, L' = SMe2 (2), O(CH2)4 (3); L = PPh3, L' = SMe2 (4), O(CH2)4 (5)). An X-raycrystallographic study of 2 established that one of the exopolyhedral SMe2 groups is bondedto a boron in a -site with respect to the carbon in the 5-7-CB10H11)] (L =CO, PPh3, CNBut) treated with NCMe and CF3SO3Me afford complexes [Fe(CO)2(L)(5-9-{(E)-N(Me)=C(H)Me}-7-CB10H10)] (L = CO (8), PPh3 (9), CNBut (10)). An X-ray diffractionstudy on 8 established that the iminium group was attached to a -B atom of the CB4 iron-bonded ring. Compound 8 is readily hydrolyzed in the presence of a base catalyst affording[Fe(CO)3(5-9-NH2Me-7-CB10H10)] (12), and with [Na][BH3CN] yields [Fe(CO)3(5-9-{NH(Me)Et}-7-CB10H10)] (13), the structure of which was determined by X-ray diffraction. Thereaction between [N(PPh3)2][Fe(CO)3(5-7-CB10H11)] and ButCCH gives [N(PPh3)2][Fe(CO)3(2:5-8-{(E)-C(H)=C(H)But}-7-CB10H10)] (14), which with NCMe in CF3SO3Me affords [Fe(CO)2(2:5-8-{(E)-C(H)=C(H)But}-10-{(E)-N(Me)=C(H)Me}-7-CB10H9)] (16). The site ofattachment of the exopolyhedral iminium and tert-butylvinyl substituents to the cage wasestablished by X-ray diffraction.