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The dynamic behavior of the exohedral transition metal complexes of \(\mathrm{B}_{40}: {\upeta}^{6}\)- and \({\upeta}^{7}\)-\(\mathrm{B}_{40}\hbox {Cr(CO)}_{3}\) and \(\hbox {Cr(CO)}_{3}\)-\({\upeta}^{7}\)-\(\hbox {B}_{40}\) -\({\upeta}^{7}\)-\(\hbox {Cr(CO)}_{3}\)

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Abstract

The dynamic nature of the exohedral \({\upeta}^{6}\)- and the \({\upeta}^{7}\)-complexes of \(\hbox {B}_{40}\) with \(\hbox {Cr(CO)}_{3}\) has been explored using density functional theory. The ab initio molecular dynamic simulations were performed at 1200 K to investigate the fluxionality of the heptagonal and hexagonal faces of exohedral \(\hbox {B}_{40}\) complexes. Our computations show that the coordination of the \(\hbox {B}_{40}\) faces with \(\hbox {Cr(CO)}_{3}\) fragment reduces its fluxionality to a limited extent. The activation barrier for the inter-conversion of the heptagonal and hexagonal rings in \(\hbox {(CO)}_{3}\hbox {Cr}({\upeta}^{6}\)-\(\hbox {B}_{40})\) complex is around 15.2 kcal/mol whereas in the \(\hbox {(CO)}_{3}\hbox {Cr}({\upeta}^{7}\)-\(\hbox {B}_{40})\) complex, it is slightly higher at around 19.7 kcal/mol. The coordination with another \(\hbox {Cr(CO)}_{3}\) fragment is found to be equally exergonic, with a barrier for interconversion of 21.5 kcal/mol. The HOMO-LUMO gap is almost similar as the mono-metallated complexes. The di-metallated complexes also show a dynamical behavior of the six and seven membered rings at 1200 K.

Graphical Abstract

SYNOPSIS The exohedral complexation of the seven membered rings of \(\hbox {B}_{40}\) with \(\hbox {Cr(CO)}_{3}\) increases the barrier height for interconversion of six to seven membered rings.

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Acknowledgements

The authors are thankful to Inorganic and Physical chemistry department and Supercomputer Education and Research Centre for computational facilities, Council of Scientific and Industrial Research for a Senior Research Fellowship to NK and Department of Science and Technology for the J C Bose fellowship to EDJ.

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  1. Department of Inorganic and Physical Chemistry, Indian Institute of Science, Bangalore, Karnataka, 560 012, India

    Naiwrit Karmodak & Eluvathingal D Jemmis

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  1. Naiwrit Karmodak
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  2. Eluvathingal D Jemmis
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Correspondence to Eluvathingal D Jemmis.

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Dedicated to the memory of the late Professor Charusita Chakravarty.

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Karmodak, N., Jemmis, E.D. The dynamic behavior of the exohedral transition metal complexes of \(\mathrm{B}_{40}: {\upeta}^{6}\)- and \({\upeta}^{7}\)-\(\mathrm{B}_{40}\hbox {Cr(CO)}_{3}\) and \(\hbox {Cr(CO)}_{3}\)-\({\upeta}^{7}\)-\(\hbox {B}_{40}\) -\({\upeta}^{7}\)-\(\hbox {Cr(CO)}_{3}\) . J Chem Sci 129, 1061–1067 (2017). https://doi.org/10.1007/s12039-017-1281-7

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