Bond energy M–C/H–C correlations: dual theoretical and experimental approach to the sensitivity of M–C bond strength to substituentsElectronic supplementary information (ESI) available: methods of calculation; Fig. S1: Comparison of calculated and experimental C–H bond dissociation energies for organic molecules; Table S1, comparison of calculated and experimental CO-stretching frequencies; Table S2, total energies, BDE for Re–C and H–C; Table S3, NPA charges q(C) and q(aryl) for the organic fragments C6H6

Abstract

DFT methods are used to quantify the relationship between M-C and H-C bond energies; for MLn = Re(eta5-C5H5)(CO)2H and fluorinated aryl ligands, theoretical and experimental investigations of ortho-fluorine substitution indicate a much larger increase in the M-C than in the H-C bond energy, so stabilising C-H activation products.

Computational Study of the Reaction of C6F6 with [IrMe(PEt3)3]: Identification of a Phosphine-Assisted C−F Activation Pathway via a Metallophosphorane Intermediate

“…In this context it is interesting to note the results of recent computational studies on CpRe(CO) 2 (C 6 F n H 5-n )(H) species which show that the Rearyl bond strength increases significantly with the number of ortho-F substituents that are present. 39 A similar effect appears to be in play here. 40…”

syn‐Selective Rhodium(I)‐Catalyzed Allylations of Ketimines Proceeding through a Directed CH Activation/Allene Addition Sequence

“…Whereas PPh 3 is inactive, bidentate ligands like dppe, dppp, and dppb led to the product 6 aa, although the conversions of the reactions are very low (entries 1-4). [18] The allene component 3 can also be varied and several functionalized terminal allenes participate cleanly in the cyclization event. A systematic screening led to the conclusion that both the dihedral angle of the biaryl backbone [14] and the electronic nature of the phosphorous atom have significant influence upon the reactivity of the resulting catalyst.…”

Unexpected Intermediates and Products in the C−F Bond Activation of Tetrafluorobenzenes with a Bis(triethylphosphine)Nickel Synthon: Direct Evidence of a Rapid and Reversible C−H Bond Activation by Ni(0)

“…9 In principle, this should allow for selective activation in a range of polyfluoroaromatics, but to date the selective activation of C-F bonds using nickel complexes has been limited to perfluorinated aromatics and nitrogen containing heterocycles. The reaction of (PEt 3 ) 4 Ni with pentafluorobenzene is reported to produce a mixture of products, 8 while no reactions with the tetrafluorobenzenes have been described.…”