ライフサイエンスコーパス: heterolytic

1 s were sought (stepwise radical, single-step heterolytic).

2 --> H + 1, vs. approximately 127 kcalmol for heterolytic, 1H --> H(-) + 1(+), dissociation of the OH

3 n, we introduce a cascade reaction involving heterolytic activation of 4-halopiperidines with organoa

4 Heterolytic activation of C-H bonds across Bi-O sites an

5 sistent with a catalytic mechanism involving heterolytic activation of elemental hydrogen (H(2) + Rh(

6 is pairs have found many applications in the heterolytic activation of H2 and subsequent hydrogenatio

7 he DeltaGdegrees(H-) values calculated using heterolytic activation of hydrogen are compared with tho

8 catalytic intermediates responsible for the heterolytic activation of strong element-hydrogen bonds,

9 e synthesis of a magnesium boryl through the heterolytic activation of the B-B bond of bis(pinacolato

10 That deaggregation is coupled to heterolytic Al-H bond activation at the Ru-S bond, forma

11 n reactivity are defined with respect to the heterolytic and homolytic cleavage of O-O bonds.

12 operoxide species, which then undergoes both heterolytic and homolytic cleavage to form iron(IV) pi-r

13 s of both catalysts possess nearly identical heterolytic and homolytic Co-H bond strengths for the Co

14 4)(-)) in methanol leads to products by both heterolytic and homolytic processes.

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

16 containing multiple B-H bonds depends on the heterolytic B-X bond energy.

17 : (i) to labilize the trans Al-X bond toward heterolytic behavior, and (ii) to promote the insertion

18 the increased Lewis basicity of nitrogen for heterolytic bond activation, increased ligand donor stre

19 electric field (EF) model suggests that the heterolytic bond cleavage occurs as a result of polariza

20 ates upon collision-induced activation, as a heterolytic bond cleavage reaction.

21 time, we present strong evidence for clean, heterolytic bond cleavage reactions over a metal surface

22 Our catalyst activates hydrogen via heterolytic bond cleavage, forms a monohydride, and hydr

23 inct uncaging mechanisms: photooxidation and heterolytic bond cleavage.

24 Ab initio calculations of heterolytic bond dissociation energies of the peroxyl gr

25 tron-bonded sigma-radicals with an estimated heterolytic bond dissociation energy of the S therefore

26 G3 calculations of heterolytic bond dissociation enthalpies (HBDEs) for for

27 Comparison of homolytic and heterolytic bond dissociation for tricoordinate-tricoord

28 Heterolytic bond scission is a staple of chemical reacti

29 in the proton-transfer cascade that leads to heterolytic bond scission of oxygen in P450BM-3.

30 n accelerated scission of both homolytic and heterolytic bonds, and the ring-opening of strained mech

31 The N path, in contrast, goes by heterolytic C-H activation with proton transfer to the a

32 othesis that the nitride might enable facile heterolytic C-H bond activation along the Zr-N bond, thi

33 ic studies of the second method point to the heterolytic C-H bond cleavage as the rate-determining st

34 rane and the addition of phenylacetylene via heterolytic C-H bond cleavage, further supports its nota

35 (eq) values are found to correlate best with heterolytic C-H bond strengths but in a way that is not

36 Notably, many of these show a preference for heterolytic C-H cleavage, erroneously predicting substra

37 the catalytic cycle is proposed to occur by heterolytic C-H dissociation of ethylene, which occurs a

38 s occurring by a common mechanism, involving heterolytic C-H or H-H activation via a 1,2 addition acr

39 n the NIR-II biological window and show that heterolytic C-O bond cleavage can be triggered by two SW

40 nalization without inhibiting metal-mediated heterolytic carbon-hydrogen cleavage.

41 e methods, applications, and new insights of heterolytic CC fragmentation reactions advanced over the

42 volving two Co(III)-H species and a dominant heterolytic channel in which a highly reactive Co(II)-H

43 hods, demonstrated the kinetic relevance and heterolytic character of the first C-H activation at ter

44 lysis reaction in an unusual reversal of the heterolytic chemistry that was deployed to make the same

45 issociation pathways: retrocycloaddition and heterolytic cleavage (generating a trityl cation in the

46 ond cleavage were clearly identified: a fast heterolytic cleavage (tau = 108 ps) was observed in prot

47 th the presence of the substrate retards the heterolytic cleavage and gives rise to homolytic O-OH cl

48 ct formation cis to the ReX bond followed by heterolytic cleavage at the electrophilic rhenium center

49 ane was experimentally determined versus the heterolytic cleavage energy of hydrogen in acetonitrile,

50 DFT studies reveal that this heterolytic cleavage is actually initiated by an homolyt

51 kcal/mol larger Marcus intrinsic barrier for heterolytic cleavage of 1-F than for cleavage of 1-Cl is

52 adical anion as a critical step, followed by heterolytic cleavage of a carbon-halogen bond.

53 le mechanism for biaryl formation involves a heterolytic cleavage of an aryl C-N bond and release of

54 uggest a formal stepwise mechanism involving heterolytic cleavage of an aryloxysulfur species to give

55 oxygenase (HO) enzymes could proceed through heterolytic cleavage of an iron(III)-hydroperoxo interme

56 and electrons originate from the metal (via heterolytic cleavage of an M-H bond).

57 and 4-chlorophenyltrimethylsilane caused the heterolytic cleavage of aryl-chlorine bonds to give the

58 abstraction by the ferriheme-peroxo base and heterolytic cleavage of arylhydroxylamines render molecu

59 Heterolytic cleavage of dihydrogen into a proton and a h

60 Heterolytic cleavage of H(2) by 3 at room temperature fo

61 le) based on the DFT calculations shows that heterolytic cleavage of H(2) can occur from (eta(2)-H(2)

62 dride complexes that can be generated by the heterolytic cleavage of H(2) gas to form B-H bonds.

63 3-H(2)](+) is consistent with intramolecular heterolytic cleavage of H(2) mediated by the pendant ami

64 utational studies indicate a low barrier for heterolytic cleavage of H(2).

65 bide as energetically viable relative to the heterolytic cleavage of H(2).

66 Such data signify a heterolytic cleavage of H(2)O(2) with HRP as pristine na

67 es in nature use hydrogen as a fuel, but the heterolytic cleavage of H-H bonds cannot be readily obse

68 cently been proposed to interpret the facile heterolytic cleavage of H2 by frustrated Lewis pairs (FL

69 We show how the rate of reversible heterolytic cleavage of H2 can be controlled, spanning 4

70 he dihydrogen complex and the product of the heterolytic cleavage of H2 in a functional model of the

71 We report the facile, reversible heterolytic cleavage of H2 in a manganese complex bearin

72 method involves measuring the equilibrium of heterolytic cleavage of H2 in the presence of a base, an

73 groups on N and P), have been developed for heterolytic cleavage of H2 into a proton and a hydride,

74 r 1a has been measured (49.5(1) kcal/mol) by heterolytic cleavage of H2 with Et3N in CH3CN.

75 The products of heterolytic cleavage of H2, Mo hydride complexes bearing

76 providing a design principle for controlling heterolytic cleavage of H2.

77 Our results rule out a substrate-assisted heterolytic cleavage of H2O2 en route to Cpd I.

78 l role in catalysis, acting as a base in the heterolytic cleavage of hydrogen.

79 r, Q203V PGHS-1 and PGHS-2 mutants catalyzed heterolytic cleavage of peroxides and exhibited native C

80 PGHS POX catalyzes heterolytic cleavage of primary and secondary hydroperox

81 n of charged species (even as spectators) or heterolytic cleavage of small molecules should be though

82 Direct stand breaks result from heterolytic cleavage of the adjacent C3'-carbon-oxygen b

83 consistent with an ionic mechanism involving heterolytic cleavage of the allylic C-N bond, followed b

84 deformylated substrate complex indicate that heterolytic cleavage of the C-C bond in the enzyme envir

85 Complex 4 effects the heterolytic cleavage of the C-H of phenylacetylene to yi

86 roton sources like MeOH and PhOH, the facile heterolytic cleavage of the C-OH bond in intermediate II

87 utases, which catalyze homolytic rather than heterolytic cleavage of the carbon-cobalt bond, can use

88 d by competing backward SET and irreversible heterolytic cleavage of the carbon-hydrogen bond at the

89 sm where the rate-limiting step changes from heterolytic cleavage of the carbon-oxygen bond in the al

90 (Co1+Cbl) species, which can be obtained by heterolytic cleavage of the Co-C bond in methylcobalamin

91 Heterolytic cleavage of the Co-C bonds is much more favo

92 strate for the reaction to proceed, with the heterolytic cleavage of the glycosidic C-O bond.

93 bending; (2) The bent nitrosyl promotes the heterolytic cleavage of the H-H bond and protonation of

94 ts Lewis acidic iron(II) centre promotes the heterolytic cleavage of the H-H bond and this non-redox

95 Controlling the heterolytic cleavage of the H-H bond of dihydrogen is cr

96 tion is less common due to the difficulty in heterolytic cleavage of the H-H bond.

97 city represents the free energy required for heterolytic cleavage of the metal-hydride bond to releas

98 major product of the reaction, demonstrating heterolytic cleavage of the methylcobamide carbon-cobalt

99 um hydride/cyanide species and isobutene via heterolytic cleavage of the N-Bu(t) bond.

100 A reaction mechanism of a heterolytic cleavage of the NOCF3 bond followed by recom

101 lyses point towards a mechanism in which the heterolytic cleavage of the O-O bond is triggered by a p

102 A significant amount of heterolytic cleavage of the O-O bond of cumene hydropero

103 ydroperoxoferri-HO (D140A) instead undergoes heterolytic cleavage of the O-O bond, ultimately yieldin

104 to the hydroperoxy intermediate resulting in heterolytic cleavage of the peroxide O-O bond and format

105 These radicals then undergo heterolytic cleavage of the phosphate group to yield alk

106 (4a) proceeds via a sigma-adduct followed by heterolytic cleavage of the Si-H bond and transfer of si

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

108 Heterolytic cleavage of this tyrosine radical at the Cal

109 onal models of FLP chemistry, which invoke a heterolytic cleavage pathway.

110 hosphate leaving group is then expelled in a heterolytic cleavage to give a contact alkene radical ca

111 a hydroxyl radical and Cu(II)OH rather than heterolytic cleavage to yield water and a Cu(II)-O(*-) s

112 Motifs that display heterolytic cleavage typically separate according to non

113 c cleavage via traditional Fenton chemistry, heterolytic cleavage, and nucleophilic attack.

114 orating oxygen vacancies not only drives the heterolytic cleavage, but also the homolytic cleavage of

115 nds up with H(2) coordination and subsequent heterolytic cleavage, regenerating the gold(I)-hydride a

116 rate could be converted: oxidative addition, heterolytic cleavage, sigma-bond metathesis, electrophil

117 peroxyanion and a peroxide activated toward heterolytic cleavage.

118 ide toward the proximal oxygen, facilitating heterolytic cleavage.

119 t the rate-limiting step in the reaction was heterolytic cleavage.

120 ut the hydrogen molecule is activated toward heterolytic cleavage.

121 ore "Co1+-like", a requirement to facilitate heterolytic Co-C bond cleavage.

122 he rupture of a C-C bond through concomitant heterolytic, concerted and homolytic pathways.

123 ized 'alkylator proteins' with a spectrum of heterolytic covalent-bond-forming activity (that is, rea

124 C and N isotope fractionation originate from heterolytic dechlorination of excited triplet and single

125 presumably an enzyme, capable of catalyzing heterolytic decomposition of the S-NO bond of S-nitrosoc

126 the IL points to significant involvement of heterolytic dediazoniation.

127 f the Lewis acid BPh(3), silylone 4 achieves heterolytic dihydrogen cleavage and ethylene addition to

128 Heterolytic dihydrogen cleavage proceeds neither by a (t

129 mplex in an S(N)2-like manner that induces a heterolytic dihydrogen cleavage to yield an MgOH and an

130 Its preferred heterolytic dissociation conforms with the IUPAC definit

131 pic studies, the results together point to a heterolytic dissociation mechanism of H2 over ceria, lea

132 3)H(8) proceed over Ga/H-MFI via reversible, heterolytic dissociation of C(3)H(8) at [GaH](2+) sites

133 e was obtained that the key factor promoting heterolytic dissociation was the resonance stabilization

134 ssed, homolytic dissociation is favored over heterolytic dissociation, although the distinction is sm

135 precursors led to significant enhancement of heterolytic dissociation, but inhibition was found in so

136 A corollary was that heterolytic dissociations of free radicals to yield eith

137 was employed to assess the free energies of heterolytic dissociations releasing C-centered and O-cen

138 An examination of whether the inverse heterolytic dissociations that release nucleophiles inst

139 he latter offering an unequivocal example of heterolytic E-H bond cleavage across a main group M-O bo

140 C6H5), and C-H bond rupture is promoted in a heterolytic fashion by applying standard Lewis acid/base

141 e via homolytic (Fe(IV) horizontal lineO) or heterolytic (Fe(V) horizontal lineO) fashion exclusively

142 tive C-4a-flavin alkoxide leaving group upon heterolytic fission of the peroxide bond.

143 reporting group biases reactions in favor of heterolytic fragmentation and most likely intercepts rad

144 Rate constants for heterolytic fragmentation of beta-(ester)alkyl radicals

145 The radicals undergo heterolytic fragmentation of the substituent in the beta

146 age studies showed two kinetic regimes: fast heterolytic H(2) activation directly at the MSI (E(app)

147 E(app) ~ 25 kJ/mol) and significantly slower heterolytic H(2) activation mediated by water (E(app) ~

148 atom S-to-S bridge is related to a possible heterolytic H(2) activation/production process in the en

149 e restructuring of the TiO(2) support during heterolytic H(2) adsorption; evidence for this phenomeno

150 hydride; calculated atomic charges suggest a heterolytic H(2) bond scission within the di-iridium coo

151 H NMR spectroscopy, and mechanisms involving heterolytic H(2) cleavage and elimination of [HP(i)Pr(3)

152 pair (FLP) with BPh(3), which was capable of heterolytic H(2) cleavage at 1 atm and room temperature,

153 and nickel(II) carboxylates that operate by heterolytic H(2) cleavage pathways.

154 nt CO(2) insertion appears to be faster than heterolytic H(2) production.

155 controllable switching between homolytic and heterolytic H-H bond formation pathways through molecula

156 B(C6Cl5)x(C6F5)(3-x) (x=0-3) are capable of heterolytic H2 activation in the strong-donor solvent TH

157 d example of switching between homolytic and heterolytic HER mechanisms is reported.

158 +) --> [Pd(diphosphine)(2)](+) + H*) and the heterolytic ([HPd(diphosphine)(2)](+) --> [Pd(diphosphin

159 r exemplified by aromaticity analysis of the heterolytic hydrogen cleavage reaction of ruthenium PNN

160 res surface frustrated Lewis pairs, enabling heterolytic hydrogen splitting into H(-) and H(+).

161 sfer pathways at lower current densities and heterolytic hydrogen transfer pathways at higher current

162 tive effects and plays a seminal role in the heterolytic hydrogenation mechanism.

163 Heterolytic hydrogenations, which split H(2) across a hy

164 that ZBT-1 traps I(2) molecules and induces heterolytic I-I bond cleavage.

165 Although canonical FLP chemistry is heterolytic in nature, recent work has shown that certai

166 of chemical reactions rooted in two-electron heterolytic ionic chemistry.

167 that react in a concerted or, more rarely, a heterolytic manner.

168 at Arg(38) and His(33) are important for the heterolytic mechanism at potential FFA-OOH binding sites

169 ozinc compounds should be possible through a heterolytic mechanism that involves short-lived ion pair

170 complexes split FFA-OOH predominantly via a heterolytic mechanism, yielding hydroxy-fatty acids, whe

171 arbon of the ring and subsequent single-step heterolytic migration of the substituent.

172 Reversible heterolytic N-H and H-H bond activation by MLC is shown,

173 eaction between 1 and H(2)O(2) followed by a heterolytic O-O bond cleavage facilitated by an acid-bas

174 ata, these results point to a water-assisted heterolytic O-O bond cleavage of 2 as the rate-limiting

175 I)Me(2) with cumene hydroperoxide involves a heterolytic O-O bond cleavage, implying a two-electron o

176 pathway are favored over both homolytic and heterolytic O-O bond cleavage.

177 isomerized to alpha,beta-epoxyalcohols by a heterolytic O-O cleavage mechanism with high stereoselec

178 nt of CYP 2B4 undergoes homolytic instead of heterolytic O-OH bond cleavage.

179 network that delivers protons to promote the heterolytic OO cleavage necessary for the formation of f

180 catalytic system, the occurrence of either a heterolytic or a homolytic pathway results from their co

181 are predominantly restricted to two-electron heterolytic or homolytic bond activation mechanisms.

182 lorinate the acutumine scaffold at C10 under heterolytic or radical deoxychlorination conditions led

183 (t)Bu(3)P replaces triphenylphosphine under heterolytic P-P bond scission.

184 athway normally, while it inactivates by the heterolytic path with nonoptimal substrates.

185 can cleave nonsubstrate hydroperoxides by a heterolytic path, although a homolytic course is likely

186 e, which dissociates according to a scissile heterolytic pathway and displays a pronounced mechanochr

187 Rather, a stepwise heterolytic pathway is preferred, proceeding by initial

188 lowing the distinction between homolytic and heterolytic pathways in nondestructive methods such as c

189 roducts may be underrepresented tautomers in heterolytic pathways.

190 Heterolytic phosphate release from ribose and deoxyribos

191 This transformation allowed the heterolytic photoactivation of the Ar-Cl bond in protic

192 ach to greatly increase the photolysis QY of heterolytic PPGs through stabilization of an intermediat

193 cts arose from transition structures for the heterolytic process solvated by clusters of water molecu

194 n a close-to-stoichiometric ceria surface or heterolytic products (Ce-H and OH) with the presence of

195 We find that H(2) forms in a heterolytic proton reduction step, with spin crossovers

196 d 1-methoxynaphthalene, products formed by a heterolytic reaction disappear, suggesting an electron-t

197 Rather, H2O2 forms by heterolytic reaction pathways resembling the two-electro

198 , they occurred predominantly (>53%) through heterolytic reactions.

199 iverted from arylnitrene dissociation toward heterolytic ring opening with the arylboronic acid; the

200 s for H(2) production are analyzed: one is a heterolytic route involving protonation of the hydride t

201 volving K(+) and (t)BuO(-) ions or a neutral heterolytic route involving the [KO(t)Bu]4 tetramer.

202 hemisorbed (Au-S) junctions, consistent with heterolytic S-C(sp(3)) bond cleavage and generation of a

203 hydroxysulfuranyl radical that decomposed by heterolytic S-O cleavage was thermodynamically feasible.

204 issociative electron and proton transfer and heterolytic S=O cleavage with and without a concomitant

205 r dynamics simulations are consistent with a heterolytic scission mechanism.

206 substrate, which do not only facilitate the heterolytic scission of C-H bond, but also promotes H(2)

207 rearrangements of hydroperoxides to diols by heterolytic scission of the O-O bond and insertion of th

208 site as a consequence of the proton-assisted heterolytic scission of the O-O bond of the bound peroxi

209 to the halogens, facile homolytic as well as heterolytic scission.

210 hus far, including concerted, homolytic, and heterolytic scission.

211 nds, which facilitate both the homolytic and heterolytic sigma-bond activation reactions and hydrogen

212 to determine 11 of 12 possible homolytic and heterolytic solution Co-H bond dissociation free energie

213 The mechanism of the heterolytic solvolysis of p-tolyldiazonium cation in wat

214 Heterolytic splitting and formation of H(2) takes place

215 having a computed pK(BH+) of ~57 followed by heterolytic splitting of an inert 1,2-CH bond of a benzy

216 -base pairs that trigger the low-temperature heterolytic splitting of CH(4) and H(2) to yield Al-CH(3

217 DFT calculations indicate that heterolytic splitting of dihydrogen by the FLP Rp(-)/[(T

218 etric CO2 reduction of 4a with Et3SiH led to heterolytic splitting of H2 along with formation of bis(

219 [Fe] hydrogenase (Hmd) catalyzes the heterolytic splitting of H2 by using, in its active site

220 rogenation of a biological substrate via the heterolytic splitting of molecular hydrogen.

221 by cooperative Lewis acid-base pair-mediated heterolytic splitting of the B-H bond in pinacolborane b

222 a frustrated Lewis pair mechanism involving heterolytic splitting of the C-H bond by cooperative act

223 Heterolytic splitting of the Si-H bond mediated by a Ru-