title: Spontaneous Double Hydrometallation Induced by N→M Coordination in Organometallic Hydrides of Group 14 Elements.
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]C6 H4}(-)) 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.
authors.affiliation: Department of General and Inorganic Chemistry, Faculty of Chemical Technology, University of Pardubice, Studentská 95, 53210, Pardubice, Czech Republic.
authors.forename: Miroslav
authors.initials: M
authors.lastname: Novák
authors.affiliation: Department of General and Inorganic Chemistry, Faculty of Chemical Technology, University of Pardubice, Studentská 95, 53210, Pardubice, Czech Republic.
authors.forename: Libor
authors.initials: L
authors.lastname: Dostál
authors.affiliation: Eenheid Algemene Chemie (ALGC), Member of the QCMM VUB-UGent Alliance Research Group, Vrije Universiteit Brussel, Pleinlaan 2, 1050, Brussels, Belgium. jturek@vub.ac.be.
authors.forename: Jan
authors.initials: J
authors.lastname: Turek
authors.affiliation: Eenheid Algemene Chemie (ALGC), Member of the QCMM VUB-UGent Alliance Research Group, Vrije Universiteit Brussel, Pleinlaan 2, 1050, Brussels, Belgium.
authors.forename: Mercedes
authors.initials: M
authors.lastname: Alonso
authors.affiliation: Eenheid Algemene Chemie (ALGC), Member of the QCMM VUB-UGent Alliance Research Group, Vrije Universiteit Brussel, Pleinlaan 2, 1050, Brussels, Belgium.
authors.forename: Frank
authors.initials: F
authors.lastname: De Proft
authors.affiliation: Department of General and Inorganic Chemistry, Faculty of Chemical Technology, University of Pardubice, Studentská 95, 53210, Pardubice, Czech Republic.
authors.forename: Aleš
authors.initials: A
authors.lastname: Růžička
authors.affiliation: Department of General and Inorganic Chemistry, Faculty of Chemical Technology, University of Pardubice, Studentská 95, 53210, Pardubice, Czech Republic. roman.jambor@upce.cz.
authors.forename: Roman
authors.initials: R
authors.lastname: Jambor
keywords: NMR spectroscopy; density functional calculations; group 14 elements; hydrometallation; reduction