MNDO calculations of bond strengths in alkanes

MNDO method was used to calculate 22 values of C–H bond strengths in alkanes of various structures. Results of calculation were shown to be in good agreement with the experiment. The average absolute error of calculation (without tert-butyl and cyclobutyl groups) was 1.3 kcal/mol and was comparable with experimental error of C–H bond strength determination.     

C-H stretching frequencies and C-H bond strengths of CH3X compounds

The influence of the X-group in CH₃X type molecules on the frequency of the C-H symmetrical stretching vibration has been investigated by means of normal coordinate analysis and CNDO/2 partial force constant and localized orbital calculations. The frequency of the C—H symmetrical stretching vibration was found to be dependent on the HCH angle α and the C—H symmetrical stretching force constant F_CH. By studying the partial force constants for a number of CH₃X type molecules a distinct relation between F_CH and the C—H bond length could be shown. With the help of localized orbital calculations a relation was found between the C—H bond length and the percentage ionic character of the C—H bond.     

Platinum-catalyzed aromatization of enediynes via a C-H bond insertion of tethered alkanes

[STRUCTURE: SEE TEXT] PtCl2 (5 mol%) is an effective catalyst for aromatization of enediynes via a C-H bond insertion of tethered alkanes. The reaction mechanism of this cyclization is proposed to involve platinum-pi-alkyne intermediates. This cyclization works not only for terminal alkynes but also for internal alkynes.     

Gold-mediated C-H bond functionalisation

The transition metal-catalysed direct functionalisation of C-H bonds is an increasingly viable alternative to the multi-step strategies traditionally adopted. The use of powerful and environmentally benign gold(I) and gold(III) catalysts in such transformations has highlighted their remarkable reactivity and led to a significant increase in their utilisation. This tutorial review provides an overview of gold-catalysed C-H functionalisation, looking at transformations which rely on the ability of gold to perform C-H activation, as well as those exploiting its potent π-acidity.     

C-H activation of terminal alkynes by tris-(3,5-dimethylpyrazolyl)boraterhodiumneopentylisocyanide: new metal-carbon bond strengths

C-H bond activation of terminal alkynes by [Tp'Rh(CNneopentyl)] (Tp' = hydridotris-(3,5-dimethylpyrazolyl)borate) resulted in the formation of terminal C-H bond activation products Tp'Rh(CNneopentyl)(C≡CR)H (R = t-Bu, SiMe(3), hexyl, CF(3), p-MeOC(6)H(4), Ph, and p-CF(3)C(6)H(4)). A combination of kinetic selectivity determined in competition reactions and activation energy for reductive elimination has allowed for the calculation of relative Rh-C(alkynyl) bond strengths. The bond strengths of Rh-C(alkynyl) products are noticeably higher than those of Rh-C(aryl) and Rh-C(alkyl) analogues. The relationship between M-C and C-H bond strengths showed a linear correlation (slope R(M-C/H-C) = 1.32), and follows energy correlations previously established for unsubstituted sp(2) and sp(3) C-H bonds in aliphatic and aromatic hydrocarbons.     

Zinc-catalyzed benzylic C-H bond oxidation

A zinc-catalyzed oxidation of benzylic substrates has been developed. The corresponding carbonyl containing compounds have been produced in moderate to excellent yields. Both arenes and heteroarenes can be applied as substrates by using H₂O₂ as the oxidant.     

The equilibrium C-H bond length

The equilibrium C-H bond length has been determined up to now for about 40 polyatomic molecules. These data are used to demonstrate the existence of quantitative correlations betweenr _e(C-H), isolated C-H bond stretching frequency and average distancer _g. It is also shown that ab initio calculations are often reliable to calculate the absolute value ofr _e(C-H), if an empirical correction is made. Some other correlations are also discussed. Finally, accurater _e(C-H) values are predicted for simple molecules.     

Visible-light-mediated tungsten-catalyzed C-H amination of unactivated alkanes with nitroarenes

Science China Chemistry - Alkylamines are important motifs in pharmaceutical and material sciences. The existing reports of C-H amination are limited to ammonia, diazo and azide nitrogen sources....     

If C-H bonds could talk: selective C-H bond oxidation

C-H oxidation has a long history and an ongoing presence in research at the forefront of chemistry and interrelated fields. As such, numerous highly useful articles and reviews have been written on this subject. Logically, these are generally written from the perspective of the scope and limitations of the reagents employed. This Minireview instead attempts to emphasize chemoselectivity imposed by the nature of the substrate. Consequently, many landmark discoveries in the field of C-H oxidation are not discussed, but hopefully the perspective taken herein will allow C-H oxidation reactions to be more readily incorporated into synthetic planning.     

Towards mild metal-catalyzed C-H bond activation

Functionalizing traditionally inert carbon-hydrogen bonds represents a powerful transformation in organic synthesis, providing new entries to valuable structural motifs and improving the overall synthetic efficiency. C-H bond activation, however, often necessitates harsh reaction conditions that result in functional group incompatibilities and limited substrate scope. An understanding of the reaction mechanism and rational design of experimental conditions have led to significant improvement in both selectivity and applicability. This critical review summarizes and discusses endeavours towards the development of mild C-H activation methods and wishes to trigger more research towards this goal. In addition, we examine select examples in complex natural product synthesis to demonstrate the synthetic utility of mild C-H functionalization (84 references).     

An attempt to reconcile conflicting measurements of the bond strengths in the xenon fluorides

The heats of formation of gaseous XeF₂, XeF₄ and XeF₆ were recently determined by means of bomb calorimetry and by photoionization mass spectrometry. Despite the high quality of these investigations, serious discrepancies arise upon their comparison. The calorimetric values are always higher than the corresponding photoionization numbers and the differences are always outside the quoted experimental errors. No literature explanation exists for this discrepancy. Four explanations are offered and discussed: two by H. H. Hyman and two by the author.     

C-H activation of ethers and alkanes by germylene-aryl halide complexes

Regioselective, room-temperature C-H activation of alkanes and ethers by stable germylenes and aryl halides is reported. Germylenes, Ge[CH(SiMe3)2]2 and Ge[N(SiMe3)2]2, and aryl halides, PhI, PhBr, and PhCl, have been employed. High yields of C-H activation products can be obtained through the use of high-dilution techniques.     

Dinuclear gold-catalyzed C-H bond functionalization of cyclopropenes

Science China Chemistry - We report an unprecedented C–H bond functionalization of cyclopropenes enabled by dinuclear gold catalysis. Highly selective C–H allylation, alkynylation and...     

C-H bond dissociation enthalpies in norbornane. An experimental and computational study

Gas-phase C-H bond dissociation enthalpies (BDEs) in norbornane were determined by quantum chemistry calculations and the C2-H BDE was experimentally obtained for the first time by time-resolved photoacoustic calorimetry. CBS-Q and CBS-QB3 methods were used to derive the values DH degrees (C1-H) = 449 kJ mol-1, DH degrees (C7-H) = 439 kJ mol-1, and DH degrees (C2-H) = 413 kJ mol-1. The experimental result DH degrees (C2-H) = 414.6 +/- 5.4 kJ mol-1 is in excellent agreement with the theoretical value. The trend DH degrees (C1-H) > DH degrees (C7-H) > DH degrees (C2-H) is discussed.     

Ruthenium-catalyzed direct C-H bond arylations of heteroarenes

Ruthenium-catalyzed C-H bond arylations of indoles, thiophenes, and pyrroles were accomplished in a highly chemo- and site-selective manner through the use of removable directing groups.     

C-H bond strengths and acidities in aromatic systems: effects of nitrogen incorporation in mono-, di-, and triazines

The negative ion chemistry of five azine molecules has been investigated using the combined experimental techniques of negative ion photoelectron spectroscopy to obtain electron affinities (EA) and tandem flowing afterglow-selected ion tube (FA-SIFT) mass spectrometry to obtain deprotonation enthalpies (Δ(acid)H(298)). The measured Δ(acid)H(298) for the most acidic site of each azine species is combined with the EA of the corresponding radical in a thermochemical cycle to determine the corresponding C-H bond dissociation energy (BDE). The site-specific C-H BDE values of pyridine, 1,2-diazine, 1,3-diazine, 1,4-diazine, and 1,3,5-triazine are 110.4 ± 2.0, 111.3 ± 0.7, 113.4 ± 0.7, 107.5 ± 0.4, and 107.8 ± 0.7 kcal mol(-1), respectively. The application of complementary experimental methods, along with quantum chemical calculations, to a series of nitrogen-substituted azines sheds light on the influence of nitrogen atom substitution on the strength of C-H bonds in six-membered rings.