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¹H NMR: Complex Splitting01:13

¹H NMR: Complex Splitting

1.9K
A proton M that is coupled to a proton X results in doublet signals for M. However, NMR-active nuclei can be simultaneously coupled to more than one nonequivalent nucleus. When M is coupled to a second proton A, such as in styrene oxide, each peak in the doublet is split into another doublet.
Splitting diagrams or splitting tree diagrams are routinely used to depict such complex couplings. While drawing splitting diagrams, the splitting with the larger coupling constant is usually applied...
1.9K
Hydrogen Bonds00:26

Hydrogen Bonds

133.1K
Hydrogen bonds are weak attractions between atoms that have formed other chemical bonds. One of these atoms is electronegative, like oxygen, and has a partial negative charge. The other is a hydrogen atom that has bonded with another electronegative atom and has a partial positive charge.
Hydrogen Bonds Control the World!
Because hydrogen has very weak electronegativity when it binds with a strongly electronegative atom, such as oxygen or nitrogen, electrons in the bond are unequally shared....
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Nuclear Binding Energy02:13

Nuclear Binding Energy

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The difference between the calculated and experimentally measured masses is known as the mass defect of the atom. In the case of helium-4, the mass defect indicates a “loss” in mass of 4.0331 amu – 4.0026 amu = 0.0305 amu. The loss in mass accompanying the formation of an atom from protons, neutrons, and electrons is due to the conversion of that mass into energy that is evolved as the atom forms. The nuclear binding energy is the energy produced when the atoms’ nucleons are bound...
14.8K
Paramagnetism01:30

Paramagnetism

3.0K
Paramagnets are materials with unpaired electrons that possess a finite magnetic moment. In the absence of a magnetic field, these moments are randomly oriented, and thus the net moment is zero. Under an external field, a torque acting on the moments tends to align them along the field's direction. However, the random thermal motion of electrons produces a torque opposite to the external field and tries to disorient the moments. These two competing effects align only a few moments along the...
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Atomic Orbitals02:44

Atomic Orbitals

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An atomic orbital represents the three-dimensional regions in an atom where an electron has the highest probability to reside. The radial distribution function indicates the total probability of finding an electron within the thin shell at a distance r from the nucleus. The atomic orbitals have distinct shapes which are determined by l, the angular momentum quantum number. The orbitals are often drawn with a boundary surface, enclosing densest regions of the cloud.
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The Atomic Theory of Matter02:59

The Atomic Theory of Matter

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The earliest recorded discussion of the basic structure of matter comes from ancient Greek philosophers. Leucippus and Democritus argued that all matter was composed of small, finite particles that they called atomos, meaning “indivisible.” Later, Aristotle and others came to the conclusion that matter consisted of various combinations of the four “elements” — fire, earth, air, and water — and could be infinitely divided. Interestingly, these philosophers...
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H2 結合,分裂,およびパラマグネティック鉄複合体の純水素原子移転

Demyan E Prokopchuk1, Geoffrey M Chambers1, Eric D Walter2

  • 1Center for Molecular Electrocatalysis, Pacific Northwest National Laboratory , Richland , Washington 99352 , United States.

Journal of the American Chemical Society
|January 24, 2019
PubMed
まとめ

パラマグネット性鉄複合体は水素 (H2) を結合して分裂することができる. この研究では,H2をパラマグネティック・ジヒドリド介質を含むユニークなメカニズムで割る新しい鉄複合体を詳細に説明しています.

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科学分野:

  • 有機金属化学
  • 水素活性化
  • キャタリシス

背景:

  • H2結合と分裂のための二磁性移行金属複合体はよく研究されています.
  • 類似の反応性を示すパラマグネティック複合体は希少であり,理解のギャップを示している.

研究 の 目的:

  • パラマグネティック鉄複合体のH2結合と分裂能力を調査する.
  • この新しい複合体によるH2分裂のメカニズムを解明する.

主な方法:

  • H2/D2の結合と分裂運動の溶液相研究
  • 電気化学分析と電子パラマグネティック共振 (EPR) スペクトロスコーピー
  • 機械的な洞察のための密度関数理論 (DFT) の計算.

主要な成果:

  • 平方平面 S = 1/2 FeI(P4N2) +カチオン (FeI+) は逆同位体効果で H2/D2を逆向きに結合する.
  • FeI+は,H2を純水素原子移転で割って,トランス-FeII (H) 2) +を形成する.
  • パラマグネティック・ジヒドリド中間体であるトランス-FeIII(H) 2+は,H2分裂機構の鍵として識別された.

結論:

  • この研究は,H2を活性化するパラマグネット複合体の希少な例を示している.
  • H2分裂には,分子内および分子間ステップとパラマグネティック二酸化物を含む新しいメカニズムが提案されています.
  • この発見は,移行金属複合体による水素活性化の理解に寄与する.