ライフサイエンスコーパス: covalency

1 to form metal-ligand bonds with a degree of covalency.

2 l parameters indicate significant metal-ring covalency.

3 r protons and no diminished ligand histidine covalency.

4 introduced theoretical index evaluates bond covalency.

5 5f radial expansion, known as central-field covalency.

6 is ~12%, indicating appreciable metal-ligand covalency.

7 rrelation energies that are measures of bond covalency.

8 below (PFB) was proposed to enhance actinide covalency.

9 of 4f orbitals and incorrect assessments of covalency.

10 ility issues due to weak metal-oxygen ligand covalency.

11 pecies, and in particular the role played by covalency.

12 isotropic components indicative of Fe-C bond covalency.

13 red for any metal ion prone to low or absent covalency.

14 traditionally associated with enhanced bond covalency.

15 relate to the extent of uranium-ligand bond covalency.

16 ar the structure-directing role of f-orbital covalency.

17 s a technique for estimating actinide-ligand covalency.

18 charge transfer character dictated by their covalency.

19 igation of molecular f-element chemical bond covalency.

20 are with respect to changes in metal-ligand covalency.

21 on reactivity was circumvented via increased covalency.

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

23 hibit high stabilities because of their full covalency.

24 and tune effects of energy degeneracy driven covalency.

25 nvolved owing to a relativistically enhanced covalency.

26 ces that reflect differences in axial ligand covalency.

27 he effects and trends in oxidation state and covalency.

28 ield transition energies and ground-state Cu covalencies.

29 cy influences the excited state energies and covalencies.

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

31 hemistry induces significant changes in Fe-C covalency (-50% upon 2 e(-) reduction), a conclusion fur

32 ations reveal that Ti increases metal-oxygen covalency, a potential route to increased stability, whi

33 Reversible covalency, achieved with, for instance, highly electron-

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

35 e number of localized 5 f electrons and bond covalency across the actinide series.

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

37 Covalency affords a unique set of advantages as well as

38 Covalency analysis of the Cu L(2,3)-edge data reveals th

39 Indeed, we show that covalency and a charge-transfer gap lead to an effective

40 that simultaneous minimization of both Cu-C covalency and alkyl radical size increases the rate of r

41 re is also a small reduction in metal-ligand covalency and an attendant increase in the d(x(2)-y(2))

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

43 nd natural bond orbital calculations suggest covalency and delocalization of the uranium f(2) electro

44 by the competition between energy gains from covalency and delocalization, and energy costs of double

45 ecule-based systems with strong metal-ligand covalency and electronic correlations.

46 ling a unique approach to tuning metal-anion covalency and energy of metal cation electronic states,

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

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

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

50 n of the OOH* intermediate through high Ru-O covalency and stabilize reactive Ru species against diss

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

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

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

54 capacity is associated with the strong Ge-S covalency and the high nonlinearity could arise from the

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

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

57 Ru-X covalency, and consequently, the delocalization of metal

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

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

60 nation, ligand oxidation state, aromaticity, covalency, and spin density transfer, which may serve as

61 n of catalyst size, the decrease of catalyst covalency, and the weakening of surface oxygen-binding a

62 erials could be achieved by strong TM-ligand covalency, and this conclusion provides possible opportu

63 luctuation, metal-oxygen bond distortion and covalency are difficult to visualize experimentally, esp

64 distinct variations of metal-oxygen bonding covalency are shown by the real-space charge-density dis

65 These findings highlight metal-ligand covalency as a novel design principle for elongating exc

66 ht the potential of fine-tuning metal-ligand covalency as a rational strategy for optimizing the chir

67 revealing the broad potential for reversible covalency as a strategy for chemical-probe discovery.

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

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

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

71 e that the strength of superexchange and the covalency at optimal doping are the best descriptors for

72 We report a systematic probe of covalency at the boundaries of f-block hard-metal/soft-l

73 f-orbital participation, via overlap-driven covalency, becomes dominant via short actinide-element d

74 Due to strong covalency between Cr and N, Cr(3+) ions are unusually lo

75 ned, our studies demonstrate that changes in covalency buffer against the accumulation of excess char

76 r correlation between M-Cl bond distance and covalency, but a strong correlation was established by a

77 The results provide evidence for 4f-orbital covalency by demonstrating its expression in the reactiv

78 ternative approach of improving metal-ligand covalency by introducing a less electronegative chalcoge

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

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

81 ese results suggest that strong metal-ligand covalency can be used to influence the charge-transfer p

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

83 We further identify regimes where covalency can serve to overcome weak binary binding affi

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

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

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

87 evolution in Li-rich oxide cathodes through covalency competition induced by the substitution of ele

88 ription while emphasizing high Fe CH(2) bond covalency, considerable double bond order, and thus, sub

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

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

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

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

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

94 tuitive since the Ce-F bonds display less 4f covalency despite their higher orbital overlap, and grea

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

96 ticularly the extent to which An(3+) /Ln(3+) covalency differences prevail and manifest as the f-bloc

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

98 he determination of the differential orbital covalency (DOC, the amount of metal vs ligand character

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

100 d-orbitals and a high degree of metal-ligand covalency due to metal -> ligand pai-backdonation.

101 e changes in Mn valence states and Mn-O bond covalency during redox cycles, reducing energy barriers

102 We investigate actinide covalency effects in two [AnCp(tt)(3)] (An = Th, U) comp

103 vide new directions for the study of orbital covalency effects of molecular compounds in solid-state

104 utely sensitive to perturbation of the Fe-NO covalency enhanced by the 3d-4p orbital mixing dipole in

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

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

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

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

109 gs such as sotorasib has renewed interest in covalency for rational drug design.

110 een orbital-energy-driven and overlap-driven covalency for the actinides in a relativistic regime.

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

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

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

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

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

116 ng 5f occupancy and decreasing An-O(yl) bond covalency from U to Pu.

117 pected U-B distances indicative of increased covalency give rise to measurable differences in solutio

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

119 Reversible covalency has mainly been evaluated for cysteine residue

120 However, 4f-orbital covalency has not been compellingly linked to distinctiv

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

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

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

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

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

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

127 ditional spectral fitting methods, while the covalency in [UCp(tt)(3)] is found to be previously over

128 Our work implies that covalency in actinides is complex even when dealing with

129 eoretical methods are used to investigate 4f covalency in CeF(6)(2-) and CeCl(6)(2-).

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

131 plitting, multiconfigurational behavior, and covalency in governing the reactivity and physical prope

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

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

134 ron distances suggest that metal-borohydride covalency in M(2)(H(3)BP(t)Bu(2)BH(3))(6) complexes gene

135 n-orbit coupling properties and metal-ligand covalency in molecular magnets, which has implications i

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

137 The enhanced 4f metal-ligand covalency in Pr(4+) gives rise to CF energy scales that

138 get when aiming to control the excited state covalency in square planar complexes.

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

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

141 d DFT calculations combined to benchmark the covalency in the chemical bonding of s- and f-block meta

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

143 S = 0)O(4)] configuration and non-negligible covalency in the cubane core.

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

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

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

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

148 for the conclusion that a greater degree of covalency in the ligand-cation orbital interactions aris

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

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

151 d quantification of the nature and extent of covalency in the Th-P linkages in 1-4 via Natural Bond O

152 ctroscopic analysis suggests the presence of covalency in the uranium-halide interactions arising fro

153 consequence of ligand redox noninnocence and covalency in the vanadium-aminophenol bonding.

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

155 ed on studies of equatorial and axial ligand covalency in three uranyl halides: NaRb(8)(UO(2))(5)F(19

156 i(II)->Ti(III)->Ti(IV), thus displaying more covalency in Ti(III) species.

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

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

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

160 The extent of covalency indicated from the calculations on [ThCp(tt)(3

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

162 Increased metal-ligand covalency, indicative of a stronger nephelauxetic effect

163 the RIXS spectra, we reveal how metal-ligand covalency influences the excited state energies and cova

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

165 Covalency involving the 5f orbitals is regularly invoked

166 The weaker covalency is attributed to the large energy gap between

167 Such covalency is disrupted upon deprotonation but cannot be

168 The covalency is distributed unevenly among the four PCA val

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

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

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

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

173 stronger M(O)-O covalency relative to M(T)-O covalency is found beneficial for a more thorough recons

174 This covalency is likely responsible for the stability of thi

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

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

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

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

179 Covalency is often considered to be an influential facto

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

181 When covalency is significant, MO models more precisely deter

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

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

184 roscopic studies have probed actinide-ligand covalency, largely confirming the paradigm of early acti

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

186 agnetic properties of 2 revealed that the 5f covalency leads to partially quenched anisotropy and fas

187 pure ionic bonding, where a large extent of covalency may exist.

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

189 Covalency occupies a central role in directing chemical

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

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

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

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

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

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

196 Here, we report measurement of the covalency of a terminal uranium(VI)-nitride by (15)N nuc

197 ctional Theory calculations to benchmark the covalency of actinide-phosphorus bonds, thus introducing

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

199 (2g) orbital population, and the intensified covalency of Co-O bond upon delithiation enables charge

200 er to the Fermi level, thereby enhancing the covalency of Co-O bonds to yield the reactivity.

201 Determining the nature and extent of covalency of early actinide chemical bonding is a fundam

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

203 pic methodology for in-depth studies of bond covalency of lanthanide atoms.

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

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

206 The enhanced covalency of Mn-O bond and increased electron density at

207 ghts the importance of properly defining the covalency of oxides when defining charge compensation in

208 The covalency of Sc(2)SnC including M(2)SnC is mostly contro

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

210 metal oxides, forming O(2), i.e. the greater covalency of the 4d and 5d compounds still favours O(2).

211 rly nonbonding, the decisive quantity is the covalency of the 5d acceptor orbitals that become popula

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

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

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

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

216 opologues of {Fe=C(H)Ar}(11) reveal the high covalency of the Fe-carbene bonding, leading to a more e

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

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

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

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

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

222 of Fe(2+) concurrent with an increase in the covalency of the Fe-S interactions, followed by reversib

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

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

225 We show that structural distortion and bond covalency of the intermediate gamma-phase determine the

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

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

228 ties are thought to depend critically on the covalency of the metal-ligand bond, and less importance

229 redistribution of electron density increases covalency of the N-B bond and thereby attenuates its hyd

230 of Np(IV/V) mixtures and weakened axial bond covalency of the NpO(2)(+) species sorbed onto IdP.

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

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

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

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

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

236 ng high-capacity electrodes by mediating the covalency of the TM-O interactions.

237 py played a critical role in identifying the covalency of the unoccupied orbitals of metal dithiolene

238 ute these observations to exceptionally high covalency of the Yb(3+) f orbitals in CrI(3):Yb(3+) stem

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

240 the redox versatility of vanadium, variable covalency of V-O bonds, and myriad coordination geometri

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

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

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

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

245 easured effect of variations in metal-ligand covalency on the reactivity of trivalent uranium and lan

246 ibitor binding through changes in Fe-carbide covalency or stretching/breaking of carbide-Fe bonds.

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

248 The calculations suggest a covalency ordering of No(II) > Yb(II) > Ca(II) Mg(II), c

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

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

251 This covalency perfectly explains the unusual metallic proper

252 inel oxides originates from the metal-oxygen covalency polarity in the M(T)-O-M(O) backbone.

253 e of concepts such as bonding heterogeneity, covalency, polarizability, lone pairs and different bond

254 d band center of Ni sites and increases Ni-O covalency, promoting the catalytic activity. This study

255 Improving the metal-ligand bond covalency rather than more established approaches such a

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

257 d to actinide ions because of a greater bond covalency relative to lanthanide ions.

258 A stronger M(O)-O covalency relative to M(T)-O covalency is found benefici

259 HERFD spectra reveal changes in p-d mixing (covalency) relative to the resting state between O/OH li

260 ate the M-O bond shortening with a change in covalency resulting from increased contributions to the

261 Increasing covalency slows down crystallization by six orders of ma

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

263 ield strength and metal-ligand (Fe-N(amido)) covalency that stabilizes the (3)CT state over the lowes

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

265 e demonstrate that enhancing Titanium-Oxygen covalency through pseudo-Jahn-Teller Effect distortion i

266 Metal-ligand covalency thus buffers the expected destabilization of t

267 We highlight key advantages of covalency to the POI and E3 ligase and the underlying th

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

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

270 ng more accurate assessments of metal-ligand covalency using bond distances from readily-available cr

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

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

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

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

275 re well-known for having strong metal-ligand covalency, which dictates their valence electronic struc

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

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

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

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

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

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

282 uare planar complexes and exhibit strong pai-covalency with the amido N-donors of the N3 ligand.

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

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

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

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