Synthesis of a Rhodium Complex Featuring the Rh–H–B Linkage via a Hydride Migration from Rhodium to Borane: Study on the Electronic Deviation Induced by the Presence of the Boron Moiety
收藏NIAID Data Ecosystem2026-03-07 收录
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https://figshare.com/articles/dataset/Synthesis_of_a_Rhodium_Complex_Featuring_the_Rh_H_B_Linkage_via_a_Hydride_Migration_from_Rhodium_to_Borane_Study_on_the_Electronic_Deviation_Induced_by_the_Presence_of_the_Boron_Moiety/2470321
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资源简介：
The rhodium complex [{o-(Ph2P)C6H4}2(Ph)BH]Rh(CO)(PPh3) (3-Rh) ,featuring a B–H–Rh interaction,
was synthesized
via phosphine ligand exchange between tris(triphenylphosphine)carbonylrhodium(I)
hydride, RhH(CO)(PPh3)3 (2-Rh),
and the diphosphine–borane {o-(Ph2P)C6H4}2BPh (5). In
contrast, the reaction of 5 with the iridium analogue
of 2-Rh, IrH(CO)(PPh3)3 (2-Ir), resulted in the formation of the iridium complex [{o-(Ph2P)C6H4}3B]Ir(H)(CO) (4-Ir), with a direct Ir→B interaction.
These compounds 3-Rh and 4-Ir were fully
characterized using 1H, 11B, and 31P NMR spectroscopy, X-ray diffraction analysis, and elemental analysis.
Density functional theory calculations of 3-Rh revealed
that the boron accepts a significant amount of electron density from
the Rh center through a three-center–two-electron Rh–H–B
interaction and that the presence of the boron moiety considerably
weakens the Rh–CO bond. The electronic variation induced by
the boron moiety can promote the facile CO elimination of 3-Rh. The “boron enhancement effect” observed in the catalytic
transfer hydrogenation of ethyl phenyl ketone is also reported.
创建时间：
2016-02-20
