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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

21 Heterolytic bond scission is a staple of chemical reacti

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

37 Heterolytic cleavage of dihydrogen into a proton and a h

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

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

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

41 3-H(2)](+) is consistent with intramolecular heterolytic cleavage of H(2) mediated by the pendant ami

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

57 PGHS POX catalyzes heterolytic cleavage of primary and secondary hydroperox

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

76 (4a) proceeds via a sigma-adduct followed by heterolytic cleavage of the Si-H bond and transfer of si

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

78 Heterolytic cleavage of this tyrosine radical at the Cal

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

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

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

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

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

84 ut the hydrogen molecule is activated toward heterolytic cleavage.

85 peroxyanion and a peroxide activated toward heterolytic cleavage.

86 ide toward the proximal oxygen, facilitating heterolytic cleavage.

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

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

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

90 the IL points to significant involvement of heterolytic dediazoniation.

91 Heterolytic dihydrogen cleavage proceeds neither by a (t

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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