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Bonding in diborane-metal complexes: a quantum-chemical and experimental study of complexes featuring early and late transition metals

The coordination chemistry of the doubly base-stabilised diborane(4), [HB(hpp)]2 (hpp=1,3,4,6,7,8-hexahydro-2H-pyrimido-[1,2-a]pyrimidinate), was extended by the synthesis of new late transition-metal complexes containing CuI and RhI fragments. A detailed experimental study was conducted and quantum...

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Bibliographic Details
Main Authors: Wagner, Arne (Author) , Kaifer, Elisabeth (Author) , Himmel, Hans-Jörg (Author)
Format: Article (Journal)
Language:English
Published: April 9, 2013
In: Chemistry - a European journal
Year: 2013, Volume: 19, Issue: 23, Pages: 7395-7409
ISSN:1521-3765
DOI:10.1002/chem.201300348
Online Access:Verlag, lizenzpflichtig, Volltext: https://doi.org/10.1002/chem.201300348
Verlag, lizenzpflichtig, Volltext: https://onlinelibrary.wiley.com/doi/abs/10.1002/chem.201300348
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Author Notes:Arne Wagner, Elisabeth Kaifer, and Hans-Jörg Himmel
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Summary:The coordination chemistry of the doubly base-stabilised diborane(4), [HB(hpp)]2 (hpp=1,3,4,6,7,8-hexahydro-2H-pyrimido-[1,2-a]pyrimidinate), was extended by the synthesis of new late transition-metal complexes containing CuI and RhI fragments. A detailed experimental study was conducted and quantum-chemical calculations on the metal-ligand bonding interactions for [HB(hpp)]2 complexes of Group 6, 9, 11 and 12 metals revealed the dominant BHM interactions in the case of early transition-metal fragments, whereas the BBM bonding prevails in the case of the late d-block compounds. These findings support the experimental results as reflected by the IR and NMR spectroscopic parameters of the investigated compounds. DFT calculations on [MeB(hpp)]2 and model reactions between [B2H4⋅2NMe3] and [Rh(μ-Cl)(C2H4)2] showed that the bicyclic guanidinate allows in principle for an oxidative addition of the BB bond. However, the formation of σ-complexes is thermodynamically favoured. The results point to the selective BH or BB bond-activation of diborane compounds by complexation, depending on the chosen transition-metal fragment.
Item Description:Gesehen am 23.09.2021
Physical Description:Online Resource
ISSN:1521-3765
DOI:10.1002/chem.201300348

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