A1 Refereed original research article in a scientific journal
Unusual 9 -> 10 rearrangement of the substituted cage carbon in the ferratricarbollide series. Synthesis of the isomeric complexes [2-eta(5)-(C5H5)-10-X-closo-2,1,7,10-FeC3B8H10] (where X = H2N, MeHN, Me2N, and Bu(t)HN)
Authors: Gruner B, Lehtonen A, Kivekas R, Sillanpaa R, Holub J, Teixidor F, Vinas C, Stibr B
Publisher: AMER CHEMICAL SOC
Publication year: 2000
Journal:: Inorganic Chemistry
Journal name in source: INORGANIC CHEMISTRY
Journal acronym: INORG CHEM
Volume: 39
Issue: 12
First page : 2577
Last page: 2580
Number of pages: 4
ISSN: 0020-1669
DOI: https://doi.org/10.1021/ic991375s
Abstract
Treatment of the zwitterionic amine tricarbollides of general formula 7-L-nido-7,8,9-C3B8H10 (1) (where L = Me2HN (Ic) and Bu'H2N (Id)) with [(eta(5)-C5H5)Fe(CO)(2)](2) in refluxing mesitylene resulted in the formation of a mixture of the known compounds [2-(eta(5)-C5H5)-9-X-closo-2, 1,7,9-FeC3B8H10] (2) (where X = H2N (2a), Me2N (2c), and Bu'HN (2d)) and a series of new, isomeric ferratricarbollylamines [2-(eta(5)-C5H5)-10-X-closo-2,1,7,10-FeC3B8H10] (3) (where X = H2N (3a), Me2N (39), and Bu'HN (3d)) in moderate yields. Complexes of type 3 (where X = H2N (3a), MeHN (3b), Me2N (39), and Bu'HN (3d)) were also obtained readily by heating complexes of type 2 (where X = H2N (2a), MeHN (2b), Me2N (29), Bu'HN (2d), and Bu'(Me)N (2e)) at ca. 300 degrees C for 10 min. All the complexes of type 3 contain reactive amine functions in meta positions with respect to the metal center. The observed 9 --> 10 rearrangement of the substituted cluster carbon is quite unexpected and is believed to result from higher thermodynamic stability of the 10-substituted isomers. The structures of all compounds of type 3 were established by high-field NMR spectroscopy and mass spectrometry, and that of 3d was determined by an X-ray diffraction study.
Treatment of the zwitterionic amine tricarbollides of general formula 7-L-nido-7,8,9-C3B8H10 (1) (where L = Me2HN (Ic) and Bu'H2N (Id)) with [(eta(5)-C5H5)Fe(CO)(2)](2) in refluxing mesitylene resulted in the formation of a mixture of the known compounds [2-(eta(5)-C5H5)-9-X-closo-2, 1,7,9-FeC3B8H10] (2) (where X = H2N (2a), Me2N (2c), and Bu'HN (2d)) and a series of new, isomeric ferratricarbollylamines [2-(eta(5)-C5H5)-10-X-closo-2,1,7,10-FeC3B8H10] (3) (where X = H2N (3a), Me2N (39), and Bu'HN (3d)) in moderate yields. Complexes of type 3 (where X = H2N (3a), MeHN (3b), Me2N (39), and Bu'HN (3d)) were also obtained readily by heating complexes of type 2 (where X = H2N (2a), MeHN (2b), Me2N (29), Bu'HN (2d), and Bu'(Me)N (2e)) at ca. 300 degrees C for 10 min. All the complexes of type 3 contain reactive amine functions in meta positions with respect to the metal center. The observed 9 --> 10 rearrangement of the substituted cluster carbon is quite unexpected and is believed to result from higher thermodynamic stability of the 10-substituted isomers. The structures of all compounds of type 3 were established by high-field NMR spectroscopy and mass spectrometry, and that of 3d was determined by an X-ray diffraction study.
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