ライフサイエンスコーパス: homolytic

1 d-dissociation energies (BDE >94 kcalmol for homolytic, 1H --> H + 1, vs. approximately 127 kcalmol f

2 n this reaction are generated via the direct homolytic activation of alcohol O-H bonds in an unusual

3 ed as key intermediates, generated by direct homolytic activation of alcohol O-H bonds through a prot

4 y accessible from simple amines, promote the homolytic activation of carbon-halogen bonds with a reac

5 proton-coupled electron transfer can enable homolytic activation of common organic functional groups

6 etal complexes as one-electron catalysts for homolytic activation of substrates to generate metal-ent

7 III)-based metalloradical system enables the homolytic activation of various aryl azides for the intr

8 h enzymatic and oxidative reactions, via the homolytic addition of nitrogen dioxide to a double bond

9 rization of sulfoxides that does not involve homolytic alpha-cleavage chemistry.

10 Comparison of homolytic and heterolytic bond dissociation for tricoord

11 bond results in accelerated scission of both homolytic and heterolytic bonds, and the ring-opening of

12 s, especially controllable switching between homolytic and heterolytic H-H bond formation pathways th

13 an unparalleled example of switching between homolytic and heterolytic HER mechanisms is reported.

14 rgies for this pathway are favored over both homolytic and heterolytic O-O bond cleavage.

15 or criteria allowing the distinction between homolytic and heterolytic pathways in nondestructive met

16 als were used to determine 11 of 12 possible homolytic and heterolytic solution Co-H bond dissociatio

17 2,6-dimethylbenzene 7, undergo base-promoted homolytic aromatic substitution (BHAS) with benzene to p

18 ceed through KO(t)Bu-promoted intramolecular homolytic aromatic substitution (HAS).

19 ental studies support a novel mechanism with homolytic aromatic substitution character, wherein elect

20 al chain mechanism with the key step being a homolytic aromatic substitution of the heteroaryl halide

21 ms that can use a photoinduced base-promoted homolytic aromatic substitution reaction (photo-BHAS) ha

22 actions (SRN1-type chemistry), base-promoted homolytic aromatic substitutions (BHAS), radical Heck-ty

23 +) and suggest, akin to the halogens, facile homolytic as well as heterolytic scission.

24 the Lewis acid BCl(3), we found evidence for homolytic B-Cl bond cleavage leading to formation of a b

25 Spectroscopic characterization suggests that homolytic beta-scission at the boron-carbon bond results

26 ly restricted to two-electron heterolytic or homolytic bond activation mechanisms.

27 an function as a non-classical mechanism for homolytic bond activation, providing opportunities to ge

28 olecules (MSE) and of the radicals formed by homolytic bond cleavage (RSE) and their effect on BDE ar

29 xt step, demethylation of the sulphoxide via homolytic bond cleavage leads to methyl radical formatio

30 rization, which initiates polymerization via homolytic bond cleavage of oxime ester groups attached t

31 complished by taking advantage of the facile homolytic bond cleavage of the fragile Si horizontal lin

32 ments suggest that the U-Pn bonds degrade by homolytic bond cleavage, whereas the more redox-robust t

33 uced changes in the net forward rate of C-Co homolytic bond cleavage.

34 lowed by a SET-type C-Hal activation through homolytic bond cleavage.

35 athways, including cycloadditions, selective homolytic bond cleavages and strain-release chemistry, i

36 The homolytic bond dissociation energies (BDEs(O-H)) for the

37 These calculations reveal that W-H homolytic bond dissociation energies (BDEs) decrease wit

38 The homolytic bond dissociation energies (BDEs) for the acid

39 On the basis of the homolytic bond dissociation energies (BDEs) only, the (a

40 Comparison of the C-F and C-Cl homolytic bond dissociation energies suggests that an im

41 The calculated adiabatic homolytic bond dissociation energy of this strained bond

42 The computed Co-C homolytic bond dissociation enthalpies (BDEs) of the lat

43 auling specified, describes quite accurately homolytic bond dissociation enthalpies of common covalen

44 y iodotyrosine results in loss of iodine via homolytic bond dissociation.

45 olycyclic aromatic intermediates, as well as homolytic bond fragmentation of the edge functional grou

46 egime, thus minimizing the risk of undesired homolytic bond rupture.

47 oyloxime mechanophores undergo force-induced homolytic bond scission at the N-O bond, and their mecha

48 century ago, mechanoradicals originate from homolytic bond scission in polymers.

49 pic failure level creates mechanoradicals by homolytic bond scission, similar to polymers.

50 title reagents and subsequent base-promoted homolytic C(alpha)-C(beta) cleavage leads to the formati

51 erent reaction types involving hydrocarbons (homolytic C-C bond breaking of alkanes, progressive inse

52 end groups), dissociation starts with random homolytic C-C bond cleavages along the PS chain, which l

53 tion (CAD) of [M + Ag](+) starts with random homolytic C-C bond cleavages in the PS chain, which gene

54 hanism of the photoinduced uncaging involves homolytic C-C bond fragmentation followed by radical dis

55 Thus, in this system, homolytic C-H bond cleavage involves concerted but async

56 bined in a thermodynamic cycle to afford the homolytic C-H bond dissociation energy.

57 that an electrophilic iron carbene mediates homolytic C-H cleavage and rebounds from the resulting o

58 Homolytic C-H dissociation prevails on bare (*-*) and O*

59 hat photoexcitation of aryl iodides leads to homolytic C-I bond cleavage.

60 these processes believed to proceed through homolytic C-N bond fission of the ylide, followed by rad

61 f neutral nitric oxide through a first-order homolytic C-N bond scission to release up to 88% nitric

62 , cinnamyl, and diarylmethyl, undergo facile homolytic C-N bond scission under mild conditions to giv

63 rgy by a diphenyl ether substrate results in homolytic C-O bond cleavage followed by recombination to

64 o an ion-pair intermediate that will undergo homolytic C-O bond cleavage via an approximately 11.0 kc

65 ciation chemistry is observed, including the homolytic C-S cleavage in (+3) charge state and various

66 The putative homolytic chemistry was confirmed by using 2-methyl-1-ph

67 the O-O bond of the ferric hydroperoxide for homolytic cleavage and (2) directs the resultant hydroxy

68 hanistic interpretation consisting of a Si-H homolytic cleavage and subsequent rebound to the Si-cent

69 rprints provided evidence supporting N-NO(2) homolytic cleavage as the primary initial decomposition

70 Photodissociation with 266 nm light yields homolytic cleavage at the modification site, generating

71 a single electron transfer (SET) process or homolytic cleavage by chemical methods or advanced photo

72 cycloreversion mechanism was described as a homolytic cleavage characterized by an anchimeric assist

73 oduction of hydrazine reagent that undergoes homolytic cleavage forming radical intermediate species.

74 After homolytic cleavage in the presence of alkenes or alcohol

75 ch the cofactor's Co-C bond is activated for homolytic cleavage may be operative for all base-off/His

76 The reaction was found to follow a homolytic cleavage mechanism as verified by electrospray

77 migration for extradiol cleavage and an O-O homolytic cleavage mechanism for intradiol cleavage.

78 ketoheptan-1-ol, also consistent with an O-O homolytic cleavage mechanism, and not consistent with a

79 Asn, Glu, Asp, or Lys residues augmented the homolytic cleavage of 8R-HPODE with formation of 10-hydr

80 l hydrogen atom transfer reactions, in which homolytic cleavage of a C-H bond is accomplished by a si

81 ion of a Lewis acid-base complex can lead to homolytic cleavage of a covalent bond in the Lewis acid.

82 inactivation of P450 by aldehydes occurs via homolytic cleavage of a peroxyhemiacetal intermediate to

83 tion by those aldehydes apparently occurs by homolytic cleavage of a peroxyhemiacetal intermediate to

84 Herein, we present the visible-light-induced homolytic cleavage of a Ti-C bond in a titanacyclopentad

85 lsilyl radical may be initially generated by homolytic cleavage of a weakened Si-H bond of a hypercoo

86 reaction with aerobic, aqueous photoinduced homolytic cleavage of adenosylcobalamin, indicating that

87 We report ammonia oxidation by homolytic cleavage of all three H atoms from a [Mo-NH3](

88 istribution due to a high-energy barrier for homolytic cleavage of an exo bond in the intermediate cy

89 The radicals generated by the homolytic cleavage of an X-H bond from the guanine.cytos

90 cated the generation of aryl radical through homolytic cleavage of Ar-I bonds via direct photoexcitat

91 y by different mechanisms, thereby achieving homolytic cleavage of both alpha-C-C bonds of the ketone

92 ydrogen atom transfer catalysis(5), in which homolytic cleavage of C(sp(3))-H bonds produces alkyl ra

93 basis of this evidence, it was proposed that homolytic cleavage of C-H bonds for CH(3)CN and CH(3)OH

94 function by radical mechanisms involving the homolytic cleavage of C-H or C-C bonds, i.e., biotin syn

95 2+) cluster cogenerated with 5'-dAdo* during homolytic cleavage of cluster-bound SAM.

96 is radical-based, redox pathway involves the homolytic cleavage of H(2) , in contrast to conventional

97 rives the heterolytic cleavage, but also the homolytic cleavage of H(2) to yield more active H(delta-

98 ade, whereas Fenton catalysis results in the homolytic cleavage of H(2)O(2) producing free radicals t

99 A reversible bond dissociation enthalpy for homolytic cleavage of Me-Cbl is calculated as 31 +/- 2 k

100 r while longer wavelengths of light initiate homolytic cleavage of metal-carbon bonds that, after int

101 defined with respect to the heterolytic and homolytic cleavage of O-O bonds.

102 dical (GS*), a reaction product derived from homolytic cleavage of S-nitrosoglutathione (GSNO).

103 ploits the energy of a photon to trigger the homolytic cleavage of such bonds in organic compounds.

104 deprotonation of radical cation, followed by homolytic cleavage of the alcohol OH group from the phen

105 ylium radical 1(*+) which is generated via a homolytic cleavage of the B-B bond of 3.

106 and inactivation by 12-IODE is initiated by homolytic cleavage of the C(11)-H bond.

107 n energy transfer (EnT) process, followed by homolytic cleavage of the C-I bond in the aryl iodide su

108 radicals on neutral tyrosine side chains by homolytic cleavage of the C-I bond.

109 from Lactobacillus leichmannii catalyzes the homolytic cleavage of the carbon-cobalt bond of adenosyl

110 The homolytic cleavage of the Co(III)-Ado or Co(III)-Me bond

111 Thermal treatment of the oxidized MOF causes homolytic cleavage of the Co(III)-halogen bonds, reducti

112 Visible light excitation induced homolytic cleavage of the Co-C bond and the formation of

113 Homolytic cleavage of the Co-C bond of anAdoCbl at the a

114 f the activating monocation to stimulate the homolytic cleavage of the Co-C5' bond in adenosylcobalam

115 adenosylcobalamin (coenzyme B12) results in homolytic cleavage of the Co-C5' bond, forming cob(II)al

116 Homolytic cleavage of the cobalt-carbon bond of the anal

117 ns, the 5'-deoxyadenosyl radical arises from homolytic cleavage of the cobalt-carbon bond, and it ini

118 bl-dependent enzymes accelerate the rate for homolytic cleavage of the cofactor's Co-C bond by approx

119 cobalamin, AdoCbl)-dependent enzymes promote homolytic cleavage of the cofactor's Co-C bond to initia

120 , the catalytic cycle of EAL is initiated by homolytic cleavage of the cofactor's Co-C bond, producin

121 in each case catalysis is initiated through homolytic cleavage of the cofactor's Co-C bond.

122 Absorption at naphthalene causes homolytic cleavage of the connecting carbon-sulfur bond

123 the chemistry proceeds by rate limiting Cu-O homolytic cleavage of the Cu(II)-(OOH) species, followed

124 ity, suggesting that Asn(964) may facilitate homolytic cleavage of the dioxygen bond of 9R-HPODE with

125 nction as a sensitizer, thereby facilitating homolytic cleavage of the ditin reagent.

126 During catalysis, homolytic cleavage of the Fe-C5' bond liberates 5'-dAdo(

127 w that the HNO adduct undergoes unimolecular homolytic cleavage of the H-NO bond.

128 he formation of reactive radical species via homolytic cleavage of the metal-ligand bond.

129 The radical reaction, which requires the homolytic cleavage of the Mg-CH(3) bond, cannot occur un

130 e formation of the oxon derivative, and (ii) homolytic cleavage of the N-C and C-S bonds of the organ

131 e readily generated by visible-light-induced homolytic cleavage of the N-N bond in N-nitrosamines, an

132 cal intermediate formed by an unusually mild homolytic cleavage of the N-O bond.

133 trong evidence of a grafting mechanism where homolytic cleavage of the N2(+) species occurs together

134 anism I, and the Ni-C bond length suggests a homolytic cleavage of the Ni(III)-methyl bond in the sub

135 Reactions with phenols suggest homolytic cleavage of the O-H bond to give products that

136 The nonconcerted process involving homolytic cleavage of the O-N bond in 5 was found to be

137 late ligand of the diiron centre may trigger homolytic cleavage of the O-O bond by transferring a pro

138 t the hydroxylation reaction is initiated by homolytic cleavage of the O-O bond in the C(4a)-hydroper

139 The observed homolytic cleavage of the O-O bond of 1 is explored with

140 tudies revealed that I435 is not formed upon homolytic cleavage of the O-O bond of PN, but instead ar

141 Importantly, there is a barrier for homolytic cleavage of the O-O bond on the high-spin pote

142 ough an iron(III)-bound peroxynitrite before homolytic cleavage of the O-O bond to form an iron(IV)-o

143 Homolytic cleavage of the O-O bond yields the catalytica

144 ystems show similar reactivities and undergo homolytic cleavage of the O-O bond.

145 p in the thermal decomposition of PPE is the homolytic cleavage of the oxygen-carbon bond.

146 the metal, a process triggered by an unusual homolytic cleavage of the peroxide bond, forming a disto

147 te fragmentation of the ozonide initiated by homolytic cleavage of the peroxide bridge followed by re

148 Homolytic cleavage of the pyrrole NH leads to the format

149 wed that the formation of NO(x) proceeds via homolytic cleavage of the RN-NO(2) bond in the triplet s

150 roteins generate an adenosyl radical via the homolytic cleavage of the S-C(5') bond of SAM.

151 aturase RS enzyme, HydG, results in specific homolytic cleavage of the S-CH(3) bond of SAM, rather th

152 particular, hyper-long Co-N bonds may favor homolytic cleavage of the trans-cobalt-carbon bond in th

153 imately 10(12)-fold rate acceleration of the homolytic cleavage of the upper axial cobalt-carbon bond

154 used to produce carbon-centered radicals by homolytic cleavage of their C-Co bond under mild conditi

155 Homolytic cleavage of this moiety during substrate epoxi

156 rged as a major biochemical strategy for the homolytic cleavage of unactivated C-H bonds.

157 ails are explored by DFT supporting a simple homolytic cleavage pathway from a kappa(1)-ONO bound int

158 artitions between Calpha-Cbeta oxidation and homolytic cleavage pathways.

159 ated form of BINOL via a mechanism involving homolytic cleavage prompted by the intramolecular electr

160 ation of a stable radical (by abstraction or homolytic cleavage reactions) increases the acidity of a

161 s, which then undergoes both heterolytic and homolytic cleavage to form iron(IV) pi-radical cations a

162 lporphyrins in refluxing toluene underwent a homolytic cleavage to produce nitrogen-sulfur radicals.

163 cating that a Cu(I)OOH species undergoes O-O homolytic cleavage to yield a hydroxyl radical and Cu(II

164 FeCl(3) undergoes a homolytic cleavage upon irradiation with white light to

165 re calculated for three different reactions: homolytic cleavage via traditional Fenton chemistry, het

166 tions, 1,4-dihydropyridines (DHPs) undergo a homolytic cleavage, forming exclusively a Csp(3)-centere

167 ture, which may be important in facilitating homolytic cleavage, is the long cobalt-nitrogen bond lin

168 a number of possible pathways including O-O homolytic cleavage, M-O homolytic cleavage, nucleophilic

169 thways including O-O homolytic cleavage, M-O homolytic cleavage, nucleophilic O-atom transfer, and el

170 *)Cys) was the radical-directed Calpha-Cbeta homolytic cleavage, resulting in the formation of glycyl

171 d tert-butyl hydroperoxide, t-BuOOH) undergo homolytic cleavage.

172 n rearrangement, but not able to undergo O-O homolytic cleavage.

173 -chlorophenol, via a mechanism involving O-O homolytic cleavage.

174 allylic chloride substrate followed by C-Cl homolytic cleavage.

175 at one mass unit above the mass expected for homolytic cleavage.

176 ic assistance continuum promoted by bis-beta-homolytic cleavage.

177 al (5'-dAdo*), the same radical generated by homolytic Co-C bond cleavage in B12 radical enzymes.

178 sts possess nearly identical heterolytic and homolytic Co-H bond strengths for the Co(III)H and Co(II

179 operoxides by a heterolytic path, although a homolytic course is likely taken in converting the norma

180 e upon thermal activation, namely a stepwise homolytic covalent bond cleavage with the elimination of

181 Homolytic decomposition of lipid hydroperoxides gives ri

182 C-mediated or transition metal ion-mediated homolytic decomposition of polyunsaturated omega-3 lipid

183 It undergoes homolytic decomposition to the DNA-reactive bifunctional

184 icosatetraenoic acid (15(S)-HPETE) undergoes homolytic decomposition to the DNA-reactive bifunctional

185 ifferent reaction catalyzed by the enzyme, a homolytic dehydration of the hydroperoxide to produce th

186 Their homolytic dissociation are however facile.

187 For all types of P-P bond discussed, homolytic dissociation is favored over heterolytic disso

188 s involving Ni(III) complexes generated from homolytic dissociation of disulfides/peroxides or halide

189 llenging substrates (e.g., CH(4), N(2)) in a homolytic fashion, as well as the exploration of novel r

190 where the O...O bond is found to cleave via homolytic (Fe(IV) horizontal lineO) or heterolytic (Fe(V

191 h organic radical intermediates generated by homolytic fission of coenzyme's unique cobalt-carbon bon

192 e by a 5'-deoxyadenosyl radical generated by homolytic fission of the coenzyme cobalt-carbon bond.

193 h organic radical intermediates generated by homolytic fission of the coenzyme's unique cobalt-carbon

194 acid (HO-N=N-OH) with a concomitant azo-type homolytic fission of the latter to N2 and.OH.

195 cid (HO-N=N-OH; 3) with concomitant azo-type homolytic fission to N(2) and *OH.

196 ng ab initio/DFT methods, we identified five homolytic fissions of C-C and C-O bonds and five hydroge

197 eactivity of thiooxime esters and identify a homolytic fragmentation and rearrangement mechanism.

198 Homolytic fragmentation of a hydroxyethylhydrazine radic

199 er of a photoexcited imine to facilitate the homolytic fragmentation of the cyclopropane ring and the

200 and a disulfide bond leads to excited state, homolytic fragmentation of the disulfide bond.

201 photo-Fries rearrangement, with concomitant homolytic fragmentation of the ester group and [1;3]-acy

202 -N2)[Mo(N[t-Bu]Ar)3]2, 2, and the product of homolytic fragmentation of the NN bond, NMo(N[t-Bu]Ar)3,

203 Br (nor=1-bicyclo[2.2.1]hept-1-yl) and their homolytic fragmentations were studied computationally us

204 , we report an accurate determination of the homolytic gas-phase Co-C bond dissociation energies in t

205 Deuterium labeling studies established homolytic H(2) (or D(2)) activation by Co(0) and cis add

206 g steric bulk around the Mn shuts down rapid homolytic H(2) evolution rendering the intermediate Mn h

207 pK(a) values were used to determine both the homolytic ([HPd(diphosphine)(2)](+) --> [Pd(diphosphine)

208 h the scissile C-H bond energy, indicating a homolytic hydrogen abstraction transition state.

209 d that the F429H mutant of CYP 2B4 undergoes homolytic instead of heterolytic O-OH bond cleavage.

210 rmation of a single product arising from the homolytic loss of CO followed by combination of the inte

211 This observation strongly supports a homolytic mechanism for O-O bond cleavage.

212 h a radical scavenger TEMPO do not support a homolytic mechanism.

213 indicate that sulfur incorporation promotes homolytic metal-ligand bond cleavage and facilitates H(2

214 turing reactive N-H bonds and estimate their homolytic N-H bond enthalpies (BDEN-H) via redox and aci

215 does not release NO radical via spontaneous homolytic N-NO bond fission nor freely diffuse through c

216 Mechanism for the homolytic N-O bond cleavage for acid generation was supp

217 The same homolytic nitro-carbon fragmentation can be diverted by

218 ium redox mediator substantially weakens the homolytic nitrogen-hydrogen bond strength of a Bronsted

219 ial bridging peroxide intermediate undergoes homolytic O--O bond cleavage generating a trans heme/non

220 lution of 2 in THF with white light leads to homolytic O-O bond cleavage and generation of a Fe(IV)(O

221 ound I (Cpd I), in a mechanism that involves homolytic O-O bond cleavage followed by H-abstraction fr

222 Moreover, the reaction is initiated with a homolytic O-O bond cleavage in the iron(III)-alkylperoxo

223 d, (HPX-CO2H)FeIII(OH), because odd-electron homolytic O-O bond cleavage is inhibited.

224 ylperoxo intermediate is proposed to undergo homolytic O-O bond cleavage to yield an oxoiron(IV) spec

225 res of Mn(III)-OOR decay are consistent with homolytic O-O bond scission.

226 rolytic cleavage is actually initiated by an homolytic O-O cleavage immediately followed by a proton-

227 onuclear LCu(II)(OOR) intermediate undergoes homolytic O-O cleavage to generate reactive RO(*) specie

228 roceeds via a direct 1,2-acyl migration, via homolytic O-O cleavage, or via a benzene oxide-oxepin re

229 rectly produce Cu(II)-HjLPMO9A and indicates homolytic O-O cleavage.

230 oxidation and are assumed to react only via homolytic O-O dissociation in existing kinetic models.

231 s the heterolytic cleavage and gives rise to homolytic O-OH cleavage, and (b) the Thr302/water cluste

232 y are used to install radical precursors for homolytic on-protein radical generation; to study enzyme

233 native sugar building blocks, which through homolytic (one-electron) chemistry bypasses unnecessary

234 The unprecedented homolytic opening of ozonides promoted and catalyzed by

235 Elimination could be initiated either by homolytic or by heterolytic cleavage of this bond.

236 lorobenzoyloxy group apparently derived from homolytic oxygen-oxygen bond cleavage.

237 Rather a homolytic P-C bond cleavage in the labile aryl phosphine

238 Formally, homolytic P-P bond scission occurs with diphenyldisulfid

239 d radical-trap studies are consistent with a homolytic pathway for C-X bond cleavage.

240 the allene oxide formed by selection of the homolytic pathway normally, while it inactivates by the

241 the occurrence of either a heterolytic or a homolytic pathway results from their competition as a fu

242 Cleavage of a C-C bond often follows a homolytic pathway, but some mechanophores have also been

243 is crucial for the formation of Cpd I in the homolytic pathway.

244 rough concomitant heterolytic, concerted and homolytic pathways.

245 ght; was faster than would be expected for a homolytic process given known Co-C bond dissociation ene

246 ol leads to products by both heterolytic and homolytic processes.

247 echanism of H2 over ceria, leading to either homolytic products (surface OHs) on a close-to-stoichiom

248 s of metalloradical catalysis in controlling homolytic radical reactions, the Co(II)-catalysed conver

249 ing over reactivity and stereoselectivity of homolytic radical reactions.

250 ontrolling the reactivity and selectivity of homolytic radical reactions.

251 riguing to find that mutases, which catalyze homolytic rather than heterolytic cleavage of the carbon

252 ted with the two pathways indicates that the homolytic reaction (Co(III)H + Co(III)H --> 2 Co(II) + H

253 e enthalpy and entropy of activation for the homolytic reaction (deltaH = -1.2 kcalmol and deltaS= -3

254 the following activation parameters for the homolytic reaction at 37 degrees C: DeltaH(f)() = 18.8 +

255 propose a modified mechanism that involves a homolytic reaction of the olefin with a copper(II)-activ

256 d the gas phase occurred exclusively through homolytic reactions, while in methanol, they occurred pr

257 ediates that control subsequent one-electron homolytic reactions.

258 However, although rare, radical (homolytic) reactions are much more common than electroph

259 3)S(0) radical that undergoes regioselective homolytic reductive cleavage of the S-C5' bond to genera

260 paths and propose a mechanism involving the homolytic reductive elimination of hydrogen.

261 n mechanisms, the VC and EC moieties undergo homolytic ring opening from their respective reduction i

262 hydrogen by two competing pathways: a slower homolytic route involving two Co(III)-H species and a do

263 ain conformational change to orchestrate the homolytic rupture of the Co-C bond.

264 es not impact significantly on the Co-C bond homolytic rupture, rendering it unusually stable, and th

265 ntral question: what controls regioselective homolytic S-C bond cleavage upon SAM reduction?

266 dinated S-adenosylmethionine (SAM) to induce homolytic S-C5' bond cleavage.

267 d electron transfer to SAM with accompanying homolytic S-C5' bond cleavage.

268 , and provides the first direct evidence for homolytic S-CH(3) bond cleavage in a RS enzyme.

269 o 31 for pK(a) values, 43 to 68 kcal/mol for homolytic SBDFEs, and 44 to 84 kcal/mol for hydride dono

270 eveal that mechanical stress facilitates the homolytic scission of the C-N bond of Katritzky's salts,

271 deoxyadenosyl radical through enzyme-induced homolytic scission of the Co-C bond.

272 ion of O-sialyl hydroxylamines by reversible homolytic scission of the glycosidic bond following the

273 cals with heme iron (Fe(III)), followed by a homolytic scission of the N-O bond and transfer of the n

274 tional modes by tunneling electrons leads to homolytic Si-Si bond rupture.

275 de electrochemical potentials, pK(a) values, homolytic solution bond dissociation free energies (SBDF

276 For comparison, the calculated homolytic strength of the N--NO bond is 40.0 kcal/mol (M

277 consistent with a regiospecific bimolecular homolytic substitution (S(H)2') mechanism proceeding thr

278 binding to a Ni(II) center, and bimolecular homolytic substitution (S(H)2) at a high-valent nickel-a

279 The development of bimolecular homolytic substitution (S(H)2) catalysis has expanded cr

280 Bimolecular homolytic substitution (S(H)2) is an open-shell mechanis

281 In contrast, the bimolecular homolytic substitution (S(H)2) mechanism offers a unique

282 is forced to take an alternative route: the homolytic substitution (S(H)2) of the sulfide sulfur by

283 n combines the fragments using a bimolecular homolytic substitution (S(H)2) reaction.

284 re thought to occur by concerted bimolecular homolytic substitution (S(H)2), and the third one, *CN t

285 ernative bond-forming mechanism, bimolecular homolytic substitution (S(H)2), as an outer sphere pathw

286 suggesting the possibility of intramolecular homolytic substitution at sulfonyl sulfur may be explain

287 On this basis, it is concluded that homolytic substitution at sulfonyl sulfur, if possible a

288 oposed to proceed via a stepwise associative homolytic substitution at the Pd center of 1 with format

289 strate that propargyl radicals could undergo homolytic substitution at zinc.

290 Here we report the use of bimolecular homolytic substitution catalysis to sort an electrophili

291 ical, a sequence of hydrogen abstraction and homolytic substitution is precisely orchestrated by the

292 t to proceed through radical chains in which homolytic substitution of a disulfide by an NHC-boryl ra

293 allyl and pentadienyl peroxyl radicals, and homolytic substitution of carbon radicals on the peroxid

294 However, their reactivity in homolytic substitution processes is strongly reduced whe

295 ction thermochemistry prove that bimolecular homolytic substitution, S(H)2, of the acetamide radical

296 pport that, in the case of iodo derivatives, homolytic thienyl-I bond fragmentation occurs first and

297 e generation of transient alkyl radicals via homolytic Ti-C bond cleavage was developed by employing

298 of cobalamin influences both the mode (i.e., homolytic vs heterolytic) and the rate of Co-C bond clea

299 Homolytic W-H bond dissociation free energies are 59.3(3

300 the hydrogen-atom donors, but not the lowest homolytic X-H (X = heavy atom) bond dissociation energie