Ionic hydrogen bond and deprotonation of cationic hydride [(η5-C5Me5)2OsH]+A−

Epstein, Lina M.; Shubina, Elena S.; Крылов, А. Н.; Kreindlin, A. Z.; Rybinskaya, M. I.

doi:10.1016/0022-328x(93)80362-f

Cited by 6 publications

(4 citation statements)

References 3 publications

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“…The structural parameters and spectroscopic features of hydrogen bonds involving transition-metal hydrides as proton donors, MH δ+ ···Y, are, in general, similar to those of classical hydrogen bonds. ,, The formation of such hydrogen bonds between a cationic hydride (e.g., [Cp* 2 OsH] + or [WH 5 (dppe) 2 ] + ) and trifluoroacetate anion as a proton acceptor causes the ν OCO bands to shift by 20–25 cm –1 . − Involvement of the metal-hydride bond in the interaction with the base was confirmed by the lower-frequency shift of ν MH bands in the presence of excess base (e.g., Δν OsH = −25 cm –1 ) . Phosphine oxides are excellent bases for hydrogen-bond studies, combining high proton-accepting abilities and high hydrogen-bond-formation constants with rather low p K a (YH + ) values.…”

Section: Mh···y Hydrogen Bonds and Proton Transfer From Transition-m...mentioning

confidence: 99%

Hydrogen and Dihydrogen Bonds in the Reactions of Metal Hydrides

et al. 2016

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The dihydrogen bond-an interaction between a transition-metal or main-group hydride (M-H) and a protic hydrogen moiety (H-X)-is arguably the most intriguing type of hydrogen bond. It was discovered in the mid-1990s and has been intensively explored since then. Herein, we collate up-to-date experimental and computational studies of the structural, energetic, and spectroscopic parameters and natures of dihydrogen-bonded complexes of the form M-H···H-X, as such species are now known for a wide variety of hydrido compounds. Being a weak interaction, dihydrogen bonding entails the lengthening of the participating bonds as well as their polarization (repolarization) as a result of electron density redistribution. Thus, the formation of a dihydrogen bond allows for the activation of both the MH and XH bonds in one step, facilitating proton transfer and preparing these bonds for further transformations. The implications of dihydrogen bonding in different stoichiometric and catalytic reactions, such as hydrogen exchange, alcoholysis and aminolysis, hydrogen evolution, hydrogenation, and dehydrogenation, are discussed.

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Section: Mh···y Hydrogen Bonds and Proton Transfer From Transition-m...mentioning

confidence: 99%

Hydrogen and Dihydrogen Bonds in the Reactions of Metal Hydrides

et al. 2016

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“…Even in the “amphoteric” hydride complex [PdH(dppe) 2 ]X (X - = CF 3 SO 3 - , BF 4 - , or SbF 6 - ), which is able to donate either H - or H + , the counteranion avoids being located close to the Pd−H moiety . In one case IR investigations indicate that protonated metallocene [(η 5 -C 5 Me 5 ) 2 OsH] + undergoes ionic hydrogen interactions with several anions (CF 3 CO 2 - , CF 3 SO 3 - , BF 4 - , or PF 6 - ) …”

Section: Ion-pairing Effects In Stoichiometric Reactionsmentioning

confidence: 99%

“…62 In one case IR investigations indicate that protonated metallocene [(η 5 -C 5 Me 5 ) 2 OsH] + undergoes ionic hydrogen interactions with several anions (CF 3 CO 2 -, CF 3 SO 3 -, BF 4 -, or PF 6 -). 63 Moving a little to the right of Scheme 4 (A-B equilibrium) Morris and co-workers have shown that it is possible to take advantage of the synergistic effects of ion pairing and the intermolecular dihydrogen bond to assemble and design novel supramolecular structural types for anionic "classical" polyhydride complexes having the countercation trapped in crown ethers or cryptands. [55][56][57][58][59] In particular, they investigated [K(Q)][MH 3 (YO)(P i Pr 3 ) 2 ] (where M ) Ru or Os and Y ) C; M ) Re and Y ) N; Q ) 18-crown-6, 1-aza-18-crown-6, or 2.2.2 crypt), 56 [K(Q)][MH 5 -(P i Pr 3 ) 2 ] (where M ) Ru or Os; Q ) 18-crown-6, 1-aza-18-crown-6, or 1,10-diaza-18-crown-6), 55,57 [K(Q)][ReH 6 -(PR 3 ) 2 ] (where R ) Cy, i Pr, Ph, or Me; Q ) 18-crown-6 or 1,10-diaza-18-crown-6), 58 and [K(Q)][IrH 4 (PR 3 ) 2 ] (where R ) Cy, i Pr, or Ph; Q ) 18-crown-6, 1-aza-18-crown-6, 1,10-diaza-18-crown-6, or 2.2.2 crypt).…”

Section: Formation and Heterolytic Splitting Of Dihydrogen Metal Comp...mentioning

confidence: 99%

Ion Pairing in Transition-Metal Organometallic Chemistry

2005

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“…This could be explained by an ion-pairing phenomenon in which the anion is closely associated with the hydride ligand and assists in the deprotonation reaction. [45][46][47] It is proposed that the interaction of the anion with the hydride ligand decreases the electron density of the hydride and helps facilitate the deprotonation by t BuOK. As the anions become larger, the approach to the hydride ligand becomes more hindered due to steric interactions with the phosphine ligands, and the ion-pairing interaction is diminished.…”

Section: Anion Effects In the Deprotonation Of Trans-[fe(dmeoprpe) 2 ...mentioning

confidence: 99%

Precursors to dinitrogen reduction: structures and reactivity of trans-[Fe(DMeOPrPE)2(η2-H2)H]+ and trans-[Fe(DMeOPrPE)2(N2)H]+

et al. 2009

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trans-[Fe(DMeOPrPE)(2)(H(2))H](+) and trans-[Fe(DMeOPrPE)(2)(N(2))H](+) (DMeOPrPE = 1,2-bis(dimethoxypropylphosphino)ethane) were synthesized and their structures determined by X-ray crystallography. These complexes are important species in a dinitrogen reduction scheme involving protonation of an iron(0) dinitrogen complex to produce ammonia. The rates of substitution of the coordinated H(2) and N(2) molecules with acetonitrile were monitored in a variety of organic solvents. The coordinated N(2) substituted approximately 6 times faster than H(2), but surprisingly the solvent had little effect on the observed rates. The results suggest that the H(2) molecule in trans-[Fe(DMeOPrPE)(2)(H(2))H](+) does not participate in hydrogen bonding to the bulk solvent, as was previously observed in the analogous Ru complex. The deprotonation of trans-[Fe(DMeOPrPE)(2)(N(2))H](+) to yield Fe(DMeOPrPE)(2)N(2) was investigated in the presence of a variety of anions, and it was found that the anion facilitates the reaction through an ion-pairing interaction in which the anion removes electron density from the hydride ligand.

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Ionic hydrogen bond and deprotonation of cationic hydride [(η5-C5Me5)2OsH]+A−

Cited by 6 publications

References 3 publications

Hydrogen and Dihydrogen Bonds in the Reactions of Metal Hydrides

Hydrogen and Dihydrogen Bonds in the Reactions of Metal Hydrides

Ion Pairing in Transition-Metal Organometallic Chemistry

Precursors to dinitrogen reduction: structures and reactivity of trans-[Fe(DMeOPrPE)2(η2-H2)H]+ and trans-[Fe(DMeOPrPE)2(N2)H]+

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