ライフサイエンスコーパス: covalency

1 on reactivity was circumvented via increased covalency.

2 l parameters indicate significant metal-ring covalency.

3 r protons and no diminished ligand histidine covalency.

4 hibit high stabilities because of their full covalency.

5 and tune effects of energy degeneracy driven covalency.

6 ium(III) species and therefore the extent of covalency.

7 nvolved owing to a relativistically enhanced covalency.

8 ces that reflect differences in axial ligand covalency.

9 ield transition energies and ground-state Cu covalencies.

10 ive to the large change in ligand-metal bond covalency (30%) observed in the data.

11 a, as well as theory, indicate a decrease in covalency across the actinide series, and the evidence p

12 This covalency-activated electronic coupling (H(DA)) facilita

13 dominantly determines the large increase in covalency and Cu-disulfide bond strength in 2.

14 hydrogen bond gains stabilization from both covalency and from the normal electrostatic interactions

15 in-orbit coupling on the competition between covalency and magnetism.

16 The T1 Cu-S covalency and potential do not change in these species r

17 e octahedral f(1) complexes to determine the covalency and strengths of the sigma and pi bonds formed

18 radical, though the spin vanishes because of covalency and strong antiferromagnetic coupling between

19 ata, a methodology for determining the total covalency and the differential orbital covalency (DOC),

20 Dy(III) complex indicate strong metal-ligand covalency and uneven donation to the Dy(III) ions by the

21 re used to assess how charge reorganization (covalency) and electrostatic interactions determine DPE

22 activity is shown to be linearly related to covalency, and M(III) oxo inductive effects on Co(IV) ox

23 clude the role of oxygen vacancies, B-O bond covalency, and redox activity of lattice oxygen species.

24 and I anions in this material exhibit strong covalency as characterized by the formation of Pb dimers

25 oordination geometry and Mo(V)-S(dithiolene) covalency as it pertains to the stability of the interme

26 exhibits a high degree of metal-ligand bond covalency as well as filled/filled pi-interactions betwe

27 From these spectra metal-ligand covalencies can be extracted using a charge-transfer mul

28 In EndoIII, this change in covalency can be quantified and makes a significant cont

29 es, all illustrating how short-range quantum covalency can overcome the powerful "shielding" oppositi

30 cies confirm the dominance of resonance-type covalency ("charge transfer") interactions over the ines

31 the D. gigas active site shows a decrease in covalency compared to the model complex, in the same oxi

32 the inverse solvent effect results from the covalency compensation from the interior thiolates.

33 ects modulate dithiolene and cysteine sulfur covalency contributions to the Mo bonding scheme.

34 that the normal solvent effect reflects the covalency decrease due to solvent H-bonding to the surfa

35 eine residue is substituted by serine, the S covalency decreases upon lyophilization which is an inve

36 creases upon water removal; similarly, HiPIP covalency decreases when unfolding exposes an otherwise

37 spect to the Cys --> Ser substitution, the S covalency decreases.

38 The covalency determined using the new MO model is in better

39 total covalency and the differential orbital covalency (DOC), that is, differences in covalency in th

40 ries manifests in orbital-mixing and, hence, covalency driven by energy degeneracy.

41 g combined with the difficultly in measuring covalency, estimating or inferring covalency often leads

42 there are almost no direct measures of such covalency for actinides.

43 s, and hence, indistinguishable Fe-imidazole covalency for both Fe-His bonds.

44 s indicates a substantially larger degree of covalency for nitrile hydratase.

45 Further, a significant increase in covalency for the Fe(III)-sulfide bond and a decrease of

46 o N(His) axial ligand and a higher degree of covalency for the ferric states relative to the ferrous

47 The data reveal an increased covalency for the S(Met) relative to N(His) axial ligand

48 org and co-workers when it was proposed that covalency from 5f-orbitals contributed to the unique beh

49 study provides a methodology for uncoupling covalency from nonlocal electrostatics, which, when coup

50 f charge transfer states with differences in covalency gives excellent fits to the data and experimen

51 Hence, the concept of covalency has potential to generate broad and substantia

52 Thus, the decrease in the covalency, hence the superexchange pathway associated wi

53 ts of DNA binding and solvation on Fe-S bond covalencies (i.e., the amount of S 3p character mixed in

54 Fe L-edges in terms of differential orbital covalency (i.e., differences in mixing of the d-orbitals

55 oscopy to determine the differential orbital covalency (i.e., the differences in the mixing of the me

56 Increased covalencies in both iron-thiolate and iron-sulfide bonds

57 the differences in orbital contributions and covalency in f-block metal-ligand bonding.

58 This observation suggests the origin of covalency in heavy actinide interactions stems from the

59 Covalency in Ln-Cl bonds of Oh-LnCl6(x-) (x = 3 for Ln =

60 ies may be used as a measure of ligand-metal covalency in molecular Ti(IV) systems in noncentrosymmet

61 The bridging ligand covalency in the [Fe2S2]+ subsite of the [Fe3S4]0 cluste

62 ng excited states with the ground state, and covalency in the Bk(IV)-O bonds that distributes the 5f

63 e transition-metal complex indicating strong covalency in the Cu-N bonds.

64 tal covalency (DOC), that is, differences in covalency in the different symmetry sets of the d orbita

65 non-heme complexes and indicates significant covalency in the Fe-oxo bond.

66 ization of the CEF interaction and degree of covalency in the ground state of actinide compounds as i

67 providing a direct measure of the degree of covalency in the halogen bond(s).

68 tion states at the manganese centers and the covalency in the metal-ligand bonding.

69 haracter (40 +/- 6%) corresponding to higher covalency in the O species compared to the P species (52

70 Evidence is presented of significant covalency in the ytterbium 4f shell of tris-cyclopentadi

71 The nature and extent of covalency in uranium bonding is still unclear compared w

72 al understanding of the nature and extent of covalency in uranium-ligand bonding, and the benefits th

73 l solvent effect is observed, that is, the S covalency increases upon lyophilization.

74 metal-centered and causes a decrease in FeNO covalency indicates that in biological systems, reductio

75 This wave function incorporates anisotropic covalency into the intra- and intermolecular ET pathways

76 Such covalency is disrupted upon deprotonation but cannot be

77 The covalency is distributed unevenly among the four PCA val

78 namely that the observed change in the Fe-S covalency is due to differences in ligand conformation b

79 Moreover, O-donor covalency is enhanced in type zero centers relative that

80 This decreased covalency is enhanced with the 1,2,3-trimethyl isomer, w

81 Kbeta mainline features and the metal-ligand covalency is established.

82 This covalency is likely responsible for the stability of thi

83 Fe-S covalency is much lower in natively hydrated Fd active s

84 Larger An-E covalency is observed in the [U(O)(E)(NR2)3](-) series,

85 ly, in EndoIII and MutY, a large increase in covalency is observed upon DNA binding, which is due to

86 A limited decrease in covalency is observed upon removal of solvent water from

87 At the same time, N-donor covalency is reduced in a similar fashion to type 1 cent

88 When covalency is significant, MO models more precisely deter

89 It is found that the sulfide covalency is significantly lower in oxidized FdI compare

90 The data reveal that the degree of covalency is similar to that which is observed in transi

91 Furthermore, differential orbital covalency leads to differences in intensity for the diff

92 The average ligand-metal bond covalencies obtained from these pre-edges are further di

93 Covalency occupies a central role in directing chemical

94 by Solomon and co-workers show that the Fe-S covalencies of [4Fe-4S] clusters in the two proteins dif

95 ronic couplings depending on the anisotropic covalencies of the donor and acceptor metal sites.

96 Experimental covalencies of the Fe-S bond for the resting low-spin an

97 are analyzed to independently determine the covalencies of the iron-sulfide and -thiolate bonds.

98 The large ground-state covalencies of the side-on complexes result in significa

99 S K-edge data give a total covalency of 28% for both Cu-S bonds in the WT protein.

100 bital energy in determining the strength and covalency of bonds formed by the f orbitals.

101 e effects on Co(IV) oxo bonding can tune the covalency of high-valent sites over a large range and th

102 electronic structure information, i.e., the covalency of metal-ligand bonds, for four iron complexes

103 entional scheme and show that increasing the covalency of metal-oxygen bonds is critical to trigger l

104 The increased covalency of Te-I bonding renders the formation of iodin

105 a series of cobaltite perovskites where the covalency of the Co-O bond and the concentration of oxyg

106 Particularly, the large covalency of the Cu-disulfide interaction in the side-on

107 Thus, the high covalency of the Cys--Cu bond allows a path through this

108 ese complexes suggest that a decrease in the covalency of the Fe-C(alkyl) interaction occurs upon red

109 y on the oxo ligand resulting from the lower covalency of the Fe-O bond.

110 ital; a longer Fe-O bond length; a decreased covalency of the Fe-O bond; and a measure of cation vaca

111 The strength and covalency of the Fe-O pi-bond result in high oxygen char

112 should vary approximately linearly with the covalency of the Fe-S bond in the oxidized state, which

113 om the backbone decreases the anisotropic pi covalency of the Fe-S bond lowering the barrier of free

114 nd, importantly, experimentally quantify the covalency of the ground-state wave function.

115 hiolate (necessary for reproducing Fe-S bond covalency of the high-spin and low-spin forms), and H-bo

116 ccupied molecular orbitals as well as to the covalency of the iron site, which reduces the total L-ed

117 the superexchange coupling constant J on the covalency of the metal ions with the bridging ligands.

118 the terminating plane, as well as increased covalency of the selenide lattice which decreases the Ni

119 change from His to Gln to Cys increases the covalency of the T1 Cu-S Cys bond and decreases its redo

120 The high covalency of the T1 Cu-S(Cys) bond is shown here to acti

121 e of the T1 Cu site and thus the anisotropic covalency of the T1 Cu-S(Cys) bond.

122 From the intensity of the preedge, the covalency of the terminal ligands is found to increase i

123 an e(g) occupancy close to unity, with high covalency of transition metal-oxygen bonds.

124 en used to determine the relative strengths (covalency) of the two axial His-Fe bonds in paramagnetic

125 measuring covalency, estimating or inferring covalency often leads to fiery debate.

126 ) model was refined to include the effect of covalency on spin orbit coupling in addition to its effe

127 uences of the sigma orbital and metal-oxygen covalency on the competition between O(2)(2-)/OH(-) disp

128 Developing a better understanding of covalency (or orbital mixing) is of fundamental importan

129 idging sulfide in the tetramer has a reduced covalency per bond (39%) as compared to the micro(2)-bri

130 These data suggest an average covalency per Cu-S bond lower than that observed for nit

131 This covalency perfectly explains the unusual metallic proper

132 This lowered bridging ligand covalency reduces the superexchange coupling parameter J

133 nalysis reveals a high degree of Mo-O(H)-N-O covalency that provides a pi-orbital pathway for one-ele

134 ides-can be ascribed to minor differences in covalency, that is, the degree to which electrons are sh

135 The changes in ligand-metal bond covalencies upon redox compared with DFT calculations in

136 The change in covalency upon redox in both the [Fe(4)S(4)](1+/2+) (fer

137 rg's 1954 hypothesis that Am(III) 5f-orbital covalency was more substantial than 4f-orbital mixing fo

138 s derived from the f orbitals; however, when covalency was small, the CF model was better than either

139 employed to directly probe ligand-metal bond covalency, where it has been found that protein active s

140 The relative barriers depend on covalency (which governs ET from Fe), and therefore vary

141 he two nitrides in each octahedron driven by covalency, which results in disordered zigzag M-N chains

142 the extent of B-site transition-metal-oxygen covalency, which serves as a secondary activity descript

143 ative measure of overlap-driven actinyl bond covalency will spark activity, and extend to numerous ap

144 y calculations support a correlation of Fe-S covalency with ease of oxidation and therefore suggest t

145 at balance the C-O bond lengths required for covalency with host-guest distances that maximize van de

146 the d-block compounds slightly decreases in covalency with increasing principal quantum number, in t

147 plexes in this transformation is buffered by covalency with the ligand, a feature of possible relevan

148 ed as quantitative measures of the An-E bond covalency within an isoelectronic series and supported s

149 tional theory studies show a large amount of covalency within the Mn-oxo bonds.

150 suggest that this nitrite-induced decreased covalency would correlate with an increased Type 2 redox