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Protonation of the Dinitrogen-Reduction Catalyst [HIPTN3N]MoIII Ivestigated by ENDOR Spectroscopy.

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Title: Protonation of the Dinitrogen-Reduction Catalyst [HIPTN3N]MoIII Ivestigated by ENDOR Spectroscopy.
Authors: Kinney, R. Adam1, McNaughton, Rebecca L.1, Jia Min Chin2, Schrock, Richard R.2 rrs@mit.edu, Hoffman, Brian M.1 bmh@northwestern.edu
Source: Inorganic Chemistry. 1/17/2011, Vol. 50 Issue 2, p418-420. 3p.
Subjects: Catalysts, Proton transfer reactions, Electron nuclear double resonance spectroscopy, Anisotropy, Deuterons, Chemical bonds
Abstract: Dinitrogen is reduced to ammonia by the molybdenum complex of L = [HIPTN3N]3- [Mo; HIPT = 3,5-(2,4,6-iPr3C6H2)2C6H3]. The mechanism by which this occurs involves the stepwise addition of proton/electron pairs, but how the first pair converts MoN2 to MoN-NH remains uncertain. The first proton of reduction might bind either at Nβ of N2 or at one of the three amido nitrogen (Nam) ligands. Treatment of MoCO with [2,4,6-Me3C5H3N]BAr′4 [Ar′ = 2,3-(CF3)2C6H3] in the absence of reductant generates HMoCO+, whose electron paramagnetic resonance spectrum has greatly reduced g anisotropy relative to MoCO. 2H Mims pulsed electron nuclear double-resonance spectroscopy of 2HMoCO+ shows a signal that simulations show to have a hyperfine tensor with an isotropic coupling, aiso(2H) = -0.22 MHz, and a roughly dipolar anisotropic interaction, T(2H) = [-0.48, -0.93, 1.42] MHz. The simulations show that the deuteron is bound to Nam, near the Mo equatorial plane, not along the normal, and at a distance of 2.6 Å from Mo, which is nearly identical with the (Nam)2H+-Mo distance predicted by density functional theory computations. [ABSTRACT FROM AUTHOR]
Copyright of Inorganic Chemistry is the property of American Chemical Society and its content may not be copied or emailed to multiple sites without the copyright holder's express written permission. Additionally, content may not be used with any artificial intelligence tools or machine learning technologies. However, users may print, download, or email articles for individual use. This abstract may be abridged. No warranty is given about the accuracy of the copy. Users should refer to the original published version of the material for the full abstract. (Copyright applies to all Abstracts.)
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  Data: Protonation of the Dinitrogen-Reduction Catalyst [HIPTN<subscript>3</subscript>N]Mo<superscript>III</superscript> Ivestigated by ENDOR Spectroscopy.
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  Data: <searchLink fieldCode="AR" term="%22Kinney%2C+R%2E+Adam%22">Kinney, R. Adam</searchLink><relatesTo>1</relatesTo><br /><searchLink fieldCode="AR" term="%22McNaughton%2C+Rebecca+L%2E%22">McNaughton, Rebecca L.</searchLink><relatesTo>1</relatesTo><br /><searchLink fieldCode="AR" term="%22Jia+Min+Chin%22">Jia Min Chin</searchLink><relatesTo>2</relatesTo><br /><searchLink fieldCode="AR" term="%22Schrock%2C+Richard+R%2E%22">Schrock, Richard R.</searchLink><relatesTo>2</relatesTo><i> rrs@mit.edu</i><br /><searchLink fieldCode="AR" term="%22Hoffman%2C+Brian+M%2E%22">Hoffman, Brian M.</searchLink><relatesTo>1</relatesTo><i> bmh@northwestern.edu</i>
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  Data: <searchLink fieldCode="JN" term="%22Inorganic+Chemistry%22">Inorganic Chemistry</searchLink>. 1/17/2011, Vol. 50 Issue 2, p418-420. 3p.
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  Data: <searchLink fieldCode="DE" term="%22Catalysts%22">Catalysts</searchLink><br /><searchLink fieldCode="DE" term="%22Proton+transfer+reactions%22">Proton transfer reactions</searchLink><br /><searchLink fieldCode="DE" term="%22Electron+nuclear+double+resonance+spectroscopy%22">Electron nuclear double resonance spectroscopy</searchLink><br /><searchLink fieldCode="DE" term="%22Anisotropy%22">Anisotropy</searchLink><br /><searchLink fieldCode="DE" term="%22Deuterons%22">Deuterons</searchLink><br /><searchLink fieldCode="DE" term="%22Chemical+bonds%22">Chemical bonds</searchLink>
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  Data: Dinitrogen is reduced to ammonia by the molybdenum complex of L = [HIPTN3N]3- [Mo; HIPT = 3,5-(2,4,6-iPr3C6H2)2C6H3]. The mechanism by which this occurs involves the stepwise addition of proton/electron pairs, but how the first pair converts MoN2 to MoN-NH remains uncertain. The first proton of reduction might bind either at Nβ of N2 or at one of the three amido nitrogen (Nam) ligands. Treatment of MoCO with [2,4,6-Me3C5H3N]BAr′4 [Ar′ = 2,3-(CF3)2C6H3] in the absence of reductant generates HMoCO+, whose electron paramagnetic resonance spectrum has greatly reduced g anisotropy relative to MoCO. 2H Mims pulsed electron nuclear double-resonance spectroscopy of 2HMoCO+ shows a signal that simulations show to have a hyperfine tensor with an isotropic coupling, aiso(2H) = -0.22 MHz, and a roughly dipolar anisotropic interaction, T(2H) = [-0.48, -0.93, 1.42] MHz. The simulations show that the deuteron is bound to Nam, near the Mo equatorial plane, not along the normal, and at a distance of 2.6 Å from Mo, which is nearly identical with the (Nam)2H+-Mo distance predicted by density functional theory computations. [ABSTRACT FROM AUTHOR]
– Name: AbstractSuppliedCopyright
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  Group: Ab
  Data: <i>Copyright of Inorganic Chemistry is the property of American Chemical Society and its content may not be copied or emailed to multiple sites without the copyright holder's express written permission. Additionally, content may not be used with any artificial intelligence tools or machine learning technologies. However, users may print, download, or email articles for individual use. This abstract may be abridged. No warranty is given about the accuracy of the copy. Users should refer to the original published version of the material for the full abstract.</i> (Copyright applies to all Abstracts.)
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        Value: 10.1021/ic102127v
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        Text: English
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      – SubjectFull: Proton transfer reactions
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      – SubjectFull: Electron nuclear double resonance spectroscopy
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      – SubjectFull: Anisotropy
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      – SubjectFull: Deuterons
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      – SubjectFull: Chemical bonds
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      – TitleFull: Protonation of the Dinitrogen-Reduction Catalyst [HIPTN3N]MoIII Ivestigated by ENDOR Spectroscopy.
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              Text: 1/17/2011
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