Relationship between H−D Spin−Spin Coupling and Internuclear Distance in Molecular Hydrogen Complexes

Hush, Noel S.

doi:10.1021/ja963150b

Cited by 42 publications

(25 citation statements)

References 18 publications

Supporting

Mentioning

Contrasting

Order By: Relevance

“…Upon coordination of a H 2 molecule into the iron site (complex 1 C2 ), the H–H bond length increases from 0.77 to 0.84 Å (Figure c). This complex ( 1 C2 ) can be classified as a “Kubas’s type (normal H 2 ) complex” , in which the interaction between two hydrogen atoms remains (i.e., the H–H bond distance is less than 1.5 Å). Furthermore, it can reversibly dissociate from the metal .…”

Section: Results and Discussionmentioning

confidence: 99%

Electron and Hydride Transfer in a Redox-Active NiFe Hydride Complex: A DFT Study

et al. 2018

View full text Add to dashboard Cite

We present mechanistic details of the formation of a NiFe hydride complex and provide information on its electron-and hydride-transfer processes on the basis of density functional theory calculations and artificial-forceinduced-reaction studies. The NiFe hydride complex conducts three transfer reactions: namely, electron transfer, hydride transfer, and proton transfer. In a NiFe hydride complex, the hydride binds to Fe, which is different from the Ni−R state in hydrogenase where the hydride is located between Ni and Fe. According to our calculations, in reaction with the ferrocenium ion, electron transfer occurs from the NiFe hydride complex to the ferrocenium ion, followed by a hydrogen atom transfer (HAT) to the second ferrocenium ion. The oxidation state of Fe varies during the redox process, different from the case of NiFe hydrogenase, where the oxidation state of Ni varies. A single-step hydride transfer occurs in the presence of a 10-methylacridinium ion (AcrH + ), which is more kinetically feasible than the HAT process. In contrast to the HAT and hydride-transfer process, the proton transfer occurs through a low barrier from a protonated diethyl ether. The revealed reaction mechanism guides the interpretation of the catalytic cycle of NiFe hydrogenase and leads to the development of efficient biomimetic catalysts for H 2 generation and an electron/hydride transfer.

show abstract

Section: Results and Discussionmentioning

confidence: 99%

Electron and Hydride Transfer in a Redox-Active NiFe Hydride Complex: A DFT Study

et al. 2018

View full text Add to dashboard Cite

show abstract

“…An essentially identical linear relationship between J H-D and d HH was predicted by quantum chemical calculations. 9 A more sophisticated analysis of the relationship between HD coupling and d HH recently reported by Chaudret, Limbach and co-workers suggests that the linearity as described in eqn. ( 1) breaks down at longer distances, but that reliable values for d HH can be extracted from H-D coupling.…”

Section: Experimental Data: Overview Of Methodologiesmentioning

confidence: 95%

Elongated dihydrogen complexes: what remains of the H–H Bond?

2004

View full text Add to dashboard Cite

Of the several hundred examples of transition metal dihydrogen complexes that have been reported to date, the vast majority have H-H distances of less than 1.0 Angstrom. A small number of complexes have been reported with distances in the range of 1.1 to 1.5 Angstrom. These complexes have been termed elongated dihydrogen complexes. In this review, experimental methods for structure determination of such complexes are summarized, along with computational approaches which have proven useful in understanding the structures of these molecules.

show abstract

“…Several authors have tried to explain the existence of elongated dihydrogen complexes and their properties with respect to the temperature dependence of the J (H,D) 1 H NMR spectrum coupling constant. About the latter issue, empirical relations exist that relate the values of the J (H,D) coupling constant with H−H distances in elongated dihydrogen complexes. 4b,, In these relations it can be seen that the magnitude of the J (H,D) coupling constant evolves inversely with the H−H distance. As for theoretical works, these complexes are notorious for the problems encountered at the theoretical level when trying to reproduce the geometry of the elongated dihydrogen ligand, even when sophisticated and costly electronic structure calculations are performed …”

Section: Introductionmentioning

confidence: 99%

Effect of the Spinning Motion of the Dihydrogen Ligand on the Properties of an Elongated Dihydrogen Complex. A Theoretical Study of the trans-[Os(H···H)Cl(H₂PCH₂CH₂PH₂)₂]⁺ Complex

et al. 1998

View full text Add to dashboard Cite

We present in this paper an electronic structure and quantum nuclear dynamics study of a modeled version of trans-[Os(H···H)Cl(dppe)2]+, an elongated dihydrogen complex classified as being between the fast and slow H2 spinning limits and whose J(H,D) coupling constant increases on increasing temperature. We have found that the librational potential energy barrier for the motion of the H2 unit is quite low, in agreement with the spinning regime of the H2 unit reported from experiment. Additionally, while the electronic structure study does not manage to describe the experimentally reported geometry obtained through neutron diffraction experiments, the quantum nuclear motion study reproduces the experimental findings very satisfactorily. Finally it is seen that only when the librational motion of the H2 unit is taken into account in an explicit way in the quantum nuclear motion calculations the temperature dependence of the J(H,D) 1H NMR coupling constant is also correctly accounted for.

show abstract

Relationship between H−D Spin−Spin Coupling and Internuclear Distance in Molecular Hydrogen Complexes

Cited by 42 publications

References 18 publications

Electron and Hydride Transfer in a Redox-Active NiFe Hydride Complex: A DFT Study

Electron and Hydride Transfer in a Redox-Active NiFe Hydride Complex: A DFT Study

Elongated dihydrogen complexes: what remains of the H–H Bond?

Effect of the Spinning Motion of the Dihydrogen Ligand on the Properties of an Elongated Dihydrogen Complex. A Theoretical Study of the trans-[Os(H···H)Cl(H₂PCH₂CH₂PH₂)₂]⁺ Complex

Contact Info

Product

Resources

About

Relationship between H−D Spin−Spin Coupling and Internuclear Distance in Molecular Hydrogen Complexes

Cited by 42 publications

References 18 publications

Electron and Hydride Transfer in a Redox-Active NiFe Hydride Complex: A DFT Study

Electron and Hydride Transfer in a Redox-Active NiFe Hydride Complex: A DFT Study

Elongated dihydrogen complexes: what remains of the H–H Bond?

Effect of the Spinning Motion of the Dihydrogen Ligand on the Properties of an Elongated Dihydrogen Complex. A Theoretical Study of the trans-[Os(H···H)Cl(H2PCH2CH2PH2)2]+ Complex

Contact Info

Product

Resources

About

Effect of the Spinning Motion of the Dihydrogen Ligand on the Properties of an Elongated Dihydrogen Complex. A Theoretical Study of the trans-[Os(H···H)Cl(H₂PCH₂CH₂PH₂)₂]⁺ Complex