Formation and Structure of a Sterically Protected Molybdenum Hydride Complex with a 15‐Electron Configuration: [(1,2,4‐C5H2tBu3)Mo(PMe3)2H]+

Baya, Miguel; Houghton, Jennifer; Daran, Jean‐Claude; Poli, Rinaldo

doi:10.1002/anie.200603628

Cited by 15 publications

(20 citation statements)

References 26 publications

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“…[27][28][29][30][31][32][33] In the mono-metallic hydride arena, EPR studies on the redox pairs of 15 and 17-electron mono-nuclear hydrido complexes have recently been reported. [34][35][36] Interestingly for some of these complexes H 2 loss can be triggered by oxidation, 35 which is clearly related, although opposite in sense, to the reductivelyinduced H 2 loss observed for the clusters described here.…”

Section: Introductionmentioning

confidence: 55%

Using EPR to follow reversible dihydrogen addition to paramagnetic clusters of high hydride count: [Rh₆(PCy₃)₆H₁₂]⁺and [Rh₆(PCy₃)₆H₁₄]⁺

et al. 2010

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A combined structural/EPR/computational chemistry investigation is reported on the two paramagnetic hydrido-cluster salts [Rh 6 4 ] EPR measurements indicate two isomers, the proportion of which change with temperature and deuteration-one axial isomer and one rhombic isomer. DFT calculations on a number of plausible isomers give EPR parameters which fit the experimentally determined rhombic isomer to one in which there is an interstitial hydride in the cluster and thirteen hydride ligands on the surface, while the axial isomer has two dihydrogen-like ligands on the cluster surface. That these isomers lie close in energy comes from both the EPR measurements (as measured from equilibrium constants over a variable temperature range) and DFT calculations. Deuteration of the hydrides should favour the isomer with the lowest zero-point energy and this is the case, with the axial isomer (two D 2 ligands on the surface) being favoured over the rhombic.

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Section: Introductionmentioning

confidence: 55%

Using EPR to follow reversible dihydrogen addition to paramagnetic clusters of high hydride count: [Rh₆(PCy₃)₆H₁₂]⁺and [Rh₆(PCy₃)₆H₁₄]⁺

et al. 2010

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“…At −80 °C, the 17-electron complex [Cp*Fe(dppe)H][PF 6 ] binds CO reversibly in CH 2 Cl 2 , cleanly forming the 19-electron adduct [Cp*Fe(dppe)(CO)H][PF 6 ] . At room temperature, addition of H 2 to [Rh 6 (PCy 3 ) 6 H 12 ][BAr F 4 ] (BAr F 4 = B(3,5-(CF 3 ) 2 C 6 H 3 ) 4 ) forms [Rh 6 (PCy 3 ) 6 H 14 ][BAr F 4 ]. − Dissociation of H 2 from the 17-electron trihydride complex [(1,2,4-( t -Bu) 3 C 5 H 2 )Mo(PMe 3 ) 2 H 3 ][PF 6 ] gave the 15-electron monohydride, [(1,2,4-( t -Bu) 3 C 5 H 2 )Mo(PMe 3 ) 2 H][PF 6 ] . The same reaction pathway was also observed for [Cp*Mo(dppe)H 3 ][PF 6 ].…”

Section: Synthesis and Stabilitymentioning

confidence: 99%

Transition-Metal Hydride Radical Cations

Shaw

Estes

et al. 2016

Chem. Rev.

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Transition-metal hydride radical cations (TMHRCs) are involved in a variety of chemical and biochemical reactions, making a more thorough understanding of their properties essential for explaining observed reactivity and for the eventual development of new applications. Generally, these species may be treated as the ones formed by one-electron oxidation of diamagnetic analogues that are neutral or cationic. Despite the importance of TMHRCs, the generally sensitive nature of these complexes has hindered their development. However, over the last four decades, many more TMHRCs have been synthesized, characterized, isolated, or hypothesized as reaction intermediates. This comprehensive review focuses on experimental studies of TMHRCs reported through the year 2014, with an emphasis on isolated and observed species. The methods used for the generation or synthesis of TMHRCs are surveyed, followed by a discussion about the stability of these complexes. The fundamental properties of TMHRCs, especially those pertaining to the M-H bond, are described, followed by a detailed treatment of decomposition pathways. Finally, reactions involving TMHRCs as intermediates are described.

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“…However, aspects of their rearrangement mechanisms and the nature of the so-called stretched dihydrogen bond, 4 Figure 1). 5,6 Unfortunately, crystallography was unable to define positions for the three crucial hydrogens in the Cp i Pr 4 complex. However, the NMR spectra 6 appear to show high similarity between the Cp t Bu 3 and Cp i Pr 4 complexes.…”

Section: ■ Introductionmentioning

confidence: 99%

Molybdenum Trihydride Complexes: Computational Determinations of Hydrogen Positions and Rearrangement Mechanisms

Szatkowski

Hall

2015

Inorg. Chem.

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In crystal structures of the molybdenum complexes [(1,2,4-C5H2(t)Bu3)Mo(PMe3)2H3] (Cp(t)Bu3) and [(C5H(i)Pr4)Mo(PMe3)2H3] (Cp(i)Pr4), the Mo-bound hydrogen positions were resolved for Cp(t)Bu3, but not for Cp(i)Pr4. NMR experiments revealed the existence of an unknown mechanism for hydrogen atom exchange in these molecules, which can be "frozen out" for Cp(t)Bu3 but not for Cp(i)Pr4. Density functional theory calculations of the most stable conformations for both complexes in the gas phase and in a continuum solvent model indicate that the H's of the Cp(i)Pr4 complex are unresloved because of their disorder, which does not occur for Cp(t)Bu3. A corresponding examination of alternative rearrangement pathways shows that the rearrangements of the H's could occur by two mechanisms: parallel to the cyclopentadienyl (Cp) ring in a single step and perpendicular to the Cp ring in two steps. The parallel pathway is preferred for both molecules, but it has a lower energy barrier for Cp(i)Pr4 than for Cp(t)Bu3.

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Formation and Structure of a Sterically Protected Molybdenum Hydride Complex with a 15‐Electron Configuration: [(1,2,4‐C₅H₂tBu₃)Mo(PMe₃)₂H]⁺

Cited by 15 publications

References 26 publications

Using EPR to follow reversible dihydrogen addition to paramagnetic clusters of high hydride count: [Rh₆(PCy₃)₆H₁₂]⁺and [Rh₆(PCy₃)₆H₁₄]⁺

Using EPR to follow reversible dihydrogen addition to paramagnetic clusters of high hydride count: [Rh₆(PCy₃)₆H₁₂]⁺and [Rh₆(PCy₃)₆H₁₄]⁺

Transition-Metal Hydride Radical Cations

Molybdenum Trihydride Complexes: Computational Determinations of Hydrogen Positions and Rearrangement Mechanisms

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Formation and Structure of a Sterically Protected Molybdenum Hydride Complex with a 15‐Electron Configuration: [(1,2,4‐C5H2tBu3)Mo(PMe3)2H]+

Cited by 15 publications

References 26 publications

Using EPR to follow reversible dihydrogen addition to paramagnetic clusters of high hydride count: [Rh6(PCy3)6H12]+and [Rh6(PCy3)6H14]+

Using EPR to follow reversible dihydrogen addition to paramagnetic clusters of high hydride count: [Rh6(PCy3)6H12]+and [Rh6(PCy3)6H14]+

Transition-Metal Hydride Radical Cations

Molybdenum Trihydride Complexes: Computational Determinations of Hydrogen Positions and Rearrangement Mechanisms

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Formation and Structure of a Sterically Protected Molybdenum Hydride Complex with a 15‐Electron Configuration: [(1,2,4‐C₅H₂tBu₃)Mo(PMe₃)₂H]⁺

Using EPR to follow reversible dihydrogen addition to paramagnetic clusters of high hydride count: [Rh₆(PCy₃)₆H₁₂]⁺and [Rh₆(PCy₃)₆H₁₄]⁺

Using EPR to follow reversible dihydrogen addition to paramagnetic clusters of high hydride count: [Rh₆(PCy₃)₆H₁₂]⁺and [Rh₆(PCy₃)₆H₁₄]⁺