342882-46-6Relevant academic research and scientific papers
Cage substitution reactions of monocarbollide carbonyl complexes of iron: Generation of iminium groups at a boron vertex
Franken, Andreas,Du, Shaowu,Jelliss, Paul A.,Kautz, Jason A.,Stone, F. Gordon A.
, p. 1597 - 1607 (2001)
Treatment of [N(PPh3)2][Fe(CO)2(L) (η5-7-CB10H11)] (L = SMe2, PPh3) in SMe2 or O(CH2)4 with H2SO4 yields the neutral charge-compensated complexes [Fe(CO)2(L)(η5-9-L′-7-CB10 H10)] (L = SMe2, L′ = SMe2 (2), O(CH2)4 (3); L = PPh3, L′ = SMe2 (4), O(CH2)4 (5)). An X-ray crystallographic study of 2 established that one of the exopolyhedral SMe2 groups is bonded to a boron in a β-site with respect to the carbon in the CBBBB ring coordinated to the iron atom. In contrast with these results, the salts [N(PPh3)2][Fe(CO)2(L) (η5-7-CB10H11)] (L = CO, PPh3, CNBut) treated with NCMe and CF3SO3Me afford complexes [Fe(CO)2(L)(η5-9-{(E)-N(Me)=C(H)Me}-7-CB10 H10)] (L = CO (8), PPh3 (9), CNBut (10)). An X-ray diffraction study on 8 established that the iminium group was attached to a β-B atom of the CB4 iron-bonded ring. Compound 8 is readily hydrolyzed in the presence of a base catalyst affording [Fe(CO)3(η5-9-NH2Me-7-CB10 H10)] (12), and with [Na][BH3CN] yields [Fe(CO)3(η5-9-{NH(Me)Et}-7-CB10 H10)] (13), the structure of which was determined by X-ray diffraction. The reaction between [N(PPh3)2][Fe(CO)3 (η5-7-CB10H11)] and ButC≡CH gives [N(PPh3)2][Fe(CO)3- (η2:η5-8-{(E)-C(H)=C(H)But} -7-CB10H10)] (14), which with NCMe in CF3SO3Me affords [Fe(CO)2(η2:η5-8-{(E)-C(H)=C(H) But}-10-{(E)-N(Me)=C(H)Me}-7-CB10H9)] (16). The site of attachment of the exopolyhedral iminium and tert-butylvinyl substituents to the cage was established by X-ray diffraction.
