Hydridic reactivity of W(CO)(H)(NO)(PMe3)3 – Dihydrogen bonding and H2 formation with protic donors

Avramović, Nataša; Höck, Jürgen; Blacque, Olivier; Fox, Thomas; Schmalle, Helmut W.; Berke, Heinz

doi:10.1016/j.jorganchem.2009.10.036

Cited by 15 publications

(15 citation statements)

References 90 publications

Supporting

Mentioning

Contrasting

Order By: Relevance

“…The rate constants and activation free energy for [WH(CO)(NO)(PMe 3 ) 3 ] reaction with proton donors vary linearly with the HA acidity (p K a ) (Figure 7). The point belonging to CF 3 CH 2 OH (not to i PrOH as stated in the original article66) falls off the trend for unknown reason. This trend confirms that the reaction rate‐determining step is proton transfer and not organyloxide coordination, similarly to that was found for [WH(CO) 2 (NO)(PMe 3 ) 2 ] (see above).…”

Section: Ion Pairing and Subsequent Transformations Of [M(η2‐h2)]+ Comentioning

confidence: 96%

“…The same trend may be expected for the related tungsten hydride WH(CO)(NO)(PMe 3 ) 3 . Indeed, variable temperature IR and NMR studies66 on the interaction between this hydride and proton donors revealed dihydrogen bond formation followed by H 2 evolution. The kinetics of the latter reaction was studied at 333 K in [D 8 ]toluene by monitoring the disappearance of the starting hydride.…”

Section: Ion Pairing and Subsequent Transformations Of [M(η2‐h2)]+ Comentioning

confidence: 98%

“… Correlations between the reaction rate constants k obs (left) and the activation free energies Δ G ‡ 333K (right) and the proton donors p K a for the reaction of [WH(CO)(NO)(PMe 3 ) 3 ] with acids in [D 8 ]toluene at 333 K. Calculated from the t 1/2 data in ref 66…”

Section: Ion Pairing and Subsequent Transformations Of [M(η2‐h2)]+ Comentioning

confidence: 99%

See 2 more Smart Citations

Dihydrogen Bonding, Proton Transfer and Beyond: What We Can Learn from Kinetics and Thermodynamics

2010

View full text Add to dashboard Cite

Hydrogen bonding to transition metal hydride complexes and its role in the proton transfer process has been a subject of the authors' research interest in recent years. The present microreview analyzes the relationships of kinetic and thermodynamic parameters of dihydrogen bonding, MH···HA, proton transfer, yielding [M(η2‐H2)] species, and subsequent steps such as [M(η2‐H2)] to [M(H)2] isomerization or H2 evolution on the basis of all data acquired so far. It aims at showing the factors that determine the stability of the species involved, the physico‐chemical (thermodynamic and kinetic) origin of the effects observed, and, ideally, allow one to better govern the hydrides reactivity.

show abstract

Section: Ion Pairing and Subsequent Transformations Of [M(η2‐h2)]+ Comentioning

confidence: 96%

Section: Ion Pairing and Subsequent Transformations Of [M(η2‐h2)]+ Comentioning

confidence: 98%

See 1 more Smart Citation

Dihydrogen Bonding, Proton Transfer and Beyond: What We Can Learn from Kinetics and Thermodynamics

2010

View full text Add to dashboard Cite

show abstract

“…The presence of nitrosyl ligands is expected to reduce the binding strength of H 2 ligands and enhance their acidity thus promoting the heterolytic splitting of H 2 . [26,27] In addition we would expect for the deprotonated dihydrogen complexes the weakening of the resulting metal-hydride bonds to facilitate hydride transfers onto unsaturated compounds. [28,29] Based on this we supposed that (diphosphane)nitrosyl complexes of the type [Mo(NO)(PʝP)(CO) 2 L][A] (L = labile ligand) might render catalytic ionic hydrogenation systems, particularly for imine hydrogenations with proton-before-hydride transfer characteristics.…”

Section: Introductionmentioning

confidence: 99%

Molybdenum Nitrosyl Complexes and Their Application in Catalytic Imine Hydrogenation Reactions

2010

Self Cite

View full text Add to dashboard Cite

The reaction between [Mo(CO)4(NO)(ClAlCl3)] and the sterically hindered diphosphanes (P∩P) 1,3‐bis(diisopropylphosphanyl)propane (dippp, a), 1,2‐bis(diisopropylphosphanyl)ethane (dippe, b), 1,1′‐bis(diisopropylphosphanyl)ferrocene (dippf, c) and 1,2‐bis(dicyclohexylphosphanyl)ethane (dcype, d) produced the chlorides [Mo(P∩P)(CO)2(NO)Cl] (1a–1d), which were transformed into the corresponding hydrides [Mo(P∩P)(CO)2(NO)H] (2a–2d) by reaction with LiBH4 in Et3N at room temperature. The molybdenum–THF complex [Mo(dippp)(CO)2(NO)(THF)][BArF4] [3a; ArF = 3,5‐(CF3)2C6H3], obtained by the reaction of 2a with [H(Et2O)2][BArF4], was exemplarily tested in the hydrogenation of the imine PhCH=N(α‐naphthyl). Replacement of the [BArF4]– counterion by the more stable [B(C6F5)4]– anion greatly increased the catalytic activity. The use of in situ mixtures of the hydrides 2a–2d and [H(Et2O)2][B(C6F5)4] improved the hydrogenation activity. The hydride 2b in combination with [H(Et2O)2][B(C6F5)4] exhibited the highest TOF value of 123 h–1 in the reduction of PhCH=N(α‐naphthyl). The hydrogenation of the imines PhCH=NPh, p‐ClC6H4CH=NPh, p‐ClC6H4CH=N‐p‐C6H4Cl, PhCH=NCH(Ph)2 and PhCH=NMes showed TOF values of 34, 74, 41, 18 and 84 h–1 at room temperatureand a H2 pressure of 30 bar. A mechanism for the ionic hydrogenation with “proton‐before‐hydride transfer” is anticipated.

show abstract

“…[5][6][7][8][9] Various groups have studied the distinctive features of DHB systems using spectroscopy, proton affinity measurements, and analysis of thermodynamic data. [10][11][12][13][14] Today, DHB has been enrolled as a pretty well-understood concept in chemical bonding whereas potential new applications of DHB is getting unfolded in many emerging areas such as hydrogen storage, water-splitting reactions, crystal engineering, catalyst tailoring and catalysis. [15][16][17] The D-H δ + • • • δ + H-A interaction, (where D and A are proton donors and acceptors, respectively) plays a crucial role in proton transfer processes and σ bond metathesis reactions.…”

Section: Introductionmentioning

confidence: 99%

Intermolecular dihydrogen bonding in VI, VII, and VIII group octahedral metal hydride complexes with water

Sandhya¹,

Remya

Suresh

2018

J Chem Sci

View full text Add to dashboard Cite

The nature of dihydrogen bonding (DHB) in VI, VII, and VIII group octahedral metal hydride complexes with H 2 O has been studied systematically using quantum theory of atoms-in-molecule (QTAIM) analysis. A dihydrogen bond (H• • •H) between hydride ligand and hydrogen of H 2 O is revealed in QTAIM analysis with the identification of a bond critical point (bcp). The DHB is due to the donation of electron density from the hydride ligand to the hydrogen of H 2 O. A strong linear correlation is observed between intermolecular H• • •H distance (d HH) and electron density (ρ) at the bcp. Structural parameters suggested the highly directional nature of DHB. Weak secondary interactions between oxygen of water and other ligands contribute significantly to the binding energy (E int) of DHB complex (2.5 to 13.2 kcal/mol). Analysis of QTAIM parameters such as kinetic-(G c), potential-(V c) and total electron energy density (H c) revealed the partially covalent character of DHB in majority of the complexes while a few of them showed closed shell character typical of purely non-covalent interactions.

show abstract

Hydridic reactivity of W(CO)(H)(NO)(PMe3)3 – Dihydrogen bonding and H2 formation with protic donors

Cited by 15 publications

References 90 publications

Dihydrogen Bonding, Proton Transfer and Beyond: What We Can Learn from Kinetics and Thermodynamics

Dihydrogen Bonding, Proton Transfer and Beyond: What We Can Learn from Kinetics and Thermodynamics

Molybdenum Nitrosyl Complexes and Their Application in Catalytic Imine Hydrogenation Reactions

Intermolecular dihydrogen bonding in VI, VII, and VIII group octahedral metal hydride complexes with water

Contact Info

Product

Resources

About