Spontaneous Double Hydrometallation Induced by N→M Coordination in Organometallic Hydrides of Group 14 Elements |
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Authors: | Miroslav Novák Dr. Libor Dostál Dr. Jan Turek Dr. Mercedes Alonso Prof. Frank De Proft Prof. Aleš Růžička Dr. Roman Jambor |
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Affiliation: | 1. Department of General and Inorganic Chemistry, Faculty of Chemical Technology, University of Pardubice, Pardubice, Czech Republic;2. Eenheid Algemene Chemie (ALGC), Member of the QCMM VUB-UGent Alliance Research Group, Vrije Universiteit Brussel, Brussels, Belgium |
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Abstract: | Our attempts to synthesise N→M intramolecularly coordinated diorganometallic hydrides L2MH2 [M=Si ( 4 ), Ge ( 5 ), Sn ( 6 )] containing the CH=N imine group (in which L is C,N‐chelating ligand {2‐[(2,6‐iPr2C6H3)N=CH]C6H4}?) yielded 1,1′‐bis(2,6‐diisopropylphenyl)‐2,2′‐spriobi[benzo[c][1,2]azasilole] ( 7 ), 1,1′‐bis(2,6‐diisopropylphenyl)‐2,2′‐spriobi[benzo[c][1,2]azagermole] ( 8 ) and C,N‐chelated homoleptic stannylene L2Sn ( 10 ), respectively. Compounds 7 and 8 are an outcome of a spontaneous double hydrometallation of the two CH=N imine moieties induced by N→M intramolecular coordination (M=Si, Ge) in the absence of any catalyst. In contrast, the diorganotin hydride L2SnH2 ( 6 ) is redox‐unstable and the reduction of the tin centre with the elimination of H2 provided the C,N‐chelated homoleptic stannylene L2Sn ( 10 ). Compounds 7 and 8 were characterised by NMR spectroscopy and X‐ray diffraction analysis. Because the proposed N→M intramolecularly coordinated diorganometallic hydrides L2MH2 [M=Si ( 4 ), Ge ( 5 ), Sn ( 6 )] revealed two different types of reduction reactions, DFT calculations were performed to gain an insight into the structures and bonding of the non‐isolable diorganometallic hydrides as well as the products of their subsequent reactions. Furthermore, the thermodynamic profiles of the different reaction pathways with respect to the central metal atom were also investigated. |
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Keywords: | density functional calculations group 14 elements hydrometallation NMR spectroscopy reduction |
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