Bonding in diborane-metal complexes

• Verfasst von: Wagner, Arne [VerfasserIn]
• Verfasst von: Kaifer, Elisabeth [VerfasserIn]
• Verfasst von: Himmel, Hans-Jörg [VerfasserIn]
• Titel: Bonding in diborane-metal complexes
• Titelzusatz: a quantum-chemical and experimental study of complexes featuring early and late transition metals
• Verf.angabe: Arne Wagner, Elisabeth Kaifer, and Hans-Jörg Himmel
• E-Jahr: 2013
• Jahr: April 9, 2013
• Umfang: 15 S.
• Teil: volume:19
• Teil: year:2013
• Teil: number:23
• Teil: pages:7395-7409
• Teil: extent:15
• Fussnoten: Gesehen am 23.09.2021
• Titel Quelle: Enthalten in: Chemistry - a European journal
• Ort Quelle: Weinheim : Wiley-VCH, 1995
• Jahr Quelle: 2013
• Band/Heft Quelle: 19(2013), 23, Seite 7395-7409
• ISSN Quelle: 1521-3765
• DOI: doi:10.1002/chem.201300348
• Datenträger: Online-Ressource
• Sprache: eng
• Sach-SW: bonding analysis
• Sach-SW: boranes
• Sach-SW: density functional calculations
• Sach-SW: NMR spectroscopy
• Sach-SW: oxidative addition
• K10plus-PPN: 1771695331

Abstract

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.