NDLI: Synthesis, structure, and reductive elimination in the series $Tp′Rh(PR_{3})(Ar^{F})H;$ Determination of rhodium – carbon bond energies of fluoroaryl substituents

Content Provider	World Health Organization (WHO)-Global Index Medicus
Author	Jones, William D. Brennessel, William W. Eisenstein, Odile Clot, Eric Tanabe, Taro
Description	Author Affiliation: Tanabe T ( Department of Chemistry, University of Rochester, Rochester, New York 14627, USA.)
Abstract	A series of complexes of the type $Tp′Rh(PR_{3})(Ar^{F})H,$ where $PR_{3}$ = PMe $_{3}$ (3) and PMe $_{2}Ph$ (9), Ar $^{F}$ = $C_{6}F_{5}$ (a), $2,3,4,5-C_{6}F_{4}H$ (b), $2,3,5,6-C_{6}F_{4}H$ (c), $2,4,6-C_{6}F_{3}H_{2}$ (d), $2,3-C_{6}F_{2}H_{3}$ (e), $2,5-C_{6}F_{2}H_{3}$ (g), and $2-C_{6}FH_{4}$ (h) and Tp′ = tris(3,5-dimethylpyrazolyl)borate , has been synthesized as stable crystalline compounds by the reactions of the $[Tp′Rh(PR_{3})]$ fragment with the corresponding fluorinated aromatic hydrocarbons, and their structures were characterized by NMR spectroscopy and elemental analysis together with X-ray crystallography . The kinetics of the reductive eliminations of fluoroarenes from complexes 3a–h in benzene- d $_{6}$ solutions at 140 °C were investigated, but were complicated by the formation of the rhodium( I) bisphosphine complex, Tp′Rh(PMe $_{3})$ $_{2}$ (4). On the other hand, thermal reactions of (9) in THF- d $_{8}$ solutions at 120 °C resulted in the formation of an intramolecular C–H bond activated complex of the phenyl group on the phosphorus atom, $Tp′Rh(κ^{2}-C_{6}H_{4}-2-PMe_{2})H$ (7), which prevents the formation of the corresponding bisphosphine complex. The experimentally determined rates of the reductive eliminations of fluoroarenes from the complexes 9a–h and their kinetic selectivities for formation in competition with the metallacycle have been used to determine relative Rh – CAr $^{F}$ bond energies. The Rh – CAr $^{F}$ bond energy is found to be dependent on the number of ortho fluorines. A plot of Rh $–CAr^{F}vs.$ C–H bond strengths resulted in a line with a slope $R^{M–C/C–H}$ of 2.15 that closely matches the DFT calculated value (slope = 2.05).
ISSN	14779226
Issue Number	43
Journal	Dalton Trans.
Volume Number	39
e-ISSN	13645447
Language	English
Publisher	Royal Society of Chemistry
Publisher Date	2010-11-21
Publisher Place	Great Britain (UK)
Access Restriction	Subscribed
Subject Keyword	Chemistry
Content Type	Text
Resource Type	Article
Subject	Inorganic Chemistry

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