The role of the inductive effect in solid state chemistry: how the chemist can use it to modify both the structural and the physical properties of the materials

Étourneau, J.; Portier, J.; Ménil, Francis

doi:10.1016/0925-8388(92)90635-m

Cited by 132 publications

(90 citation statements)

References 38 publications

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“…However, this is common for lithium-containing nitrides, and it is attributed to enhanced charge transfer (55). The inductive effect leads to short Co-N bond distances, which is observed in a valence sum for cobalt that is substantially higher than anticipated for Co' (56). These factors suggest that the parameters used for the calculation are inappropriate due to the covalent nature of nitrides.…”

Section: Bond Valence Calculationsmentioning

confidence: 84%

Synthesis, Structure, and Magnetic Properties of Sr39Co12N31

Kowach

Lin

DiSalvo

1998

Journal of Solid State Chemistry

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Section: Bond Valence Calculationsmentioning

confidence: 84%

Synthesis, Structure, and Magnetic Properties of Sr39Co12N31

Kowach

Lin

DiSalvo

1998

Journal of Solid State Chemistry

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“…[8][9][10] The substitution of barium by a lanthanide element results in the oxynitrides RTiO 2 N (R = La, Nd), [11] where the +4 oxidation state of titanium is stabilized by the inductive effect of the rare earth element on the Ti-(O,N) bond. [12,13] This well-known effect is based on the capacity of an electropositive element (alkaline earth or rare earth) to share some electrons with the closest transition metal-nitrogen (oxygen) bond to enhance its covalent character, and thus to stabilize it. NdTiO 2 N is an orthorhombic GdFeO 3 -type perovskite, while LaTiO 2 N crystallizes in a unit cell with triclinic symmetry.…”

Section: Introductionmentioning

confidence: 99%

Optical Properties of the Perovskite Solid Solution LaTiO₂N–ATiO₃(A = Sr, Ba)

2006

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Starting from the colored oxynitride LaTiO 2 N, new perovskite-type solid solutions have been evidenced in the systems La 1-x A x TiO 2+x N 1-x (A = Sr, Ba) by ammonolysis at 950°C of the corresponding oxide precursors prepared by the molten salt route. The color of the resulting powders varies progressively from the brown of LaTiO 2 N to the white of the oxide with a decrease in both the nitrogen and lanthanum contents. The optical absorption was characterized by diffuse reflectance. The nonlinear variation of the optical bandgap may result from the competition between the variation of the inductive effect between lanthanum and strontium, structural

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“…[15,22] Coincidentally, O, N, and H etc. are common surface-rich species in many catalytic processes.…”

Section: Methodsmentioning

confidence: 94%

“…3160 cm À1 for Li 2 NH vs. 3340 cm À1 for NH 3 ). More importantly, Li, as the second cation to N, executes a positive inductive effect [15] to enhance the covalent FeÀN bonding, resulting in the significantly stabilized N-rich intermediate (that is, Li 3 FeN 2 , compositionally equivalent to Li 3 N + FeN). Implied by the Brønsted-Evans-Polanyi (BEP) relationship, a reduced kinetic barrier and faster rate of reaction are expected, which is strongly supported by the abnormally high catalytic activity and low apparent activation energy of Li 2 NH-Fe 2 N compared with neat Fe 2 N (Figure 1; Supporting Information, Figure S6).…”

mentioning

confidence: 99%

Lithium Imide Synergy with 3d Transition‐Metal Nitrides Leading to Unprecedented Catalytic Activities for Ammonia Decomposition

Guo

Wang

et al. 2015

Angewandte Chemie

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Alkali metals have been widely employed as catalyst promoters; however, the promoting mechanism remains essentially unclear. Li, when in the imide form, is shown to synergize with 3d transition metals or their nitrides TM(N) spreading from Ti to Cu, leading to universal and unprecedentedly high catalytic activities in NH 3 decomposition, among which Li 2 NH À MnN has an activity superior to that of the highly active Ru/carbon nanotube catalyst. The catalysis is fulfilled via the two-step cycle comprising: 1) the reaction of Li 2 NH and 3d TM(N) to form ternary nitride of LiTMN and H 2 , and 2) the ammoniation of LiTMN to Li 2 NH, TM(N) and N 2 resulting in the neat reaction of 2 NH 3 ÐN 2 + 3 H 2 . Li 2 NH, as an NH 3 transmitting agent, favors the formation of higher Ncontent intermediate (LiTMN), where Li executes inductive effect to stabilize the TMÀN bonding and thus alters the reaction energetics.

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The role of the inductive effect in solid state chemistry: how the chemist can use it to modify both the structural and the physical properties of the materials

Cited by 132 publications

References 38 publications

Synthesis, Structure, and Magnetic Properties of Sr39Co12N31

Synthesis, Structure, and Magnetic Properties of Sr39Co12N31

Optical Properties of the Perovskite Solid Solution LaTiO₂N–ATiO₃(A = Sr, Ba)

Lithium Imide Synergy with 3d Transition‐Metal Nitrides Leading to Unprecedented Catalytic Activities for Ammonia Decomposition

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The role of the inductive effect in solid state chemistry: how the chemist can use it to modify both the structural and the physical properties of the materials

Cited by 132 publications

References 38 publications

Synthesis, Structure, and Magnetic Properties of Sr39Co12N31

Synthesis, Structure, and Magnetic Properties of Sr39Co12N31

Optical Properties of the Perovskite Solid Solution LaTiO2N–ATiO3(A = Sr, Ba)

Lithium Imide Synergy with 3d Transition‐Metal Nitrides Leading to Unprecedented Catalytic Activities for Ammonia Decomposition

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Optical Properties of the Perovskite Solid Solution LaTiO₂N–ATiO₃(A = Sr, Ba)