Macrocyclization of the semiclathrochelate o -carboranylboronate and n -butylboronate iron(II ) oximehydrazonates: synthesis and structure of clathrochelate products and unexpected allosteric effect of the apical substituent |
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Authors: | Ya. Z. Voloshin, S. Yu. Erdyakov, I. G. Makarenko, E. G. Lebed , T. V. Potapova, S. V. Svidlov, Z. A. Starikova, E. V. Pol shin, M. E. Gurskii Yu. N. Bubnov |
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Affiliation: | (1) A. N. Nesmeyanov Institute of Organoelement Compounds, Russian Academy of Sciences, 28 ul. Vavilova, 119991 Moscow, Russian Federation;(2) N. D. Zelinsky Institute of Organic Chemistry, Russian Academy of Sciences, 47 Leninsky prosp., 119991 Moscow, Russian Federation;(3) Institute of Metallophysics, National Academy of Sciences of Ukraine, 36 bulv. Vernadskogo, 03680 Kiev-142, Ukraine |
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Abstract: | The template condensation of diacetylmonooxime hydrazone (HDXO) with n-butylboronic acid and dimethyl ester of o-carboranyldiboronic acid on the iron(II) ion matrix afforded the [Fe(DXO)3(BBu)](BF4) and [Fe(DXO)3(Bo-carb)](BF4) semiclathrochelates. The H+-ion-catalyzed macrocyclization of these precursors with an excess of formaldehyde and triethyl orthoformate (TOF) resulted in the corresponding macrobicyclic complexes. In the case of o-carboranylboronate semiclathrochelate, the macrocyclization with TOF gave the clathrochelate with the previously unknown syn,syn,anti-orientation of the ethoxy substituents relative to the 1,3,5-triazacyclohexane capping fragment. The complexes obtained were characterized using elemental analysis, IR, UV-Vis, MALDI-TOF mass, 1H, 11B, and 13C NMR, and 57Fe M?ssbauer spectroscopies and X-ray crystallography. Dedicated to Academician G. A. Abakumov on the occasion of his 70th birthday. Published in Russian in Izvestiya Akademii Nauk. Seriya Khimicheskaya, No. 9, pp. 1724–1731, September, 2007. |
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Keywords: | clathrochelates iron( font-variant:small-caps" >II) organoboranes carboranes oximes hydrazonates macrocycles allosteric control X-ray crystallography |
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