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A Significant but Constrained Geometry Pt→Al Interaction: Fixation of CO2 and CS2, Activation of H2 and PhCONH2.

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Title: A Significant but Constrained Geometry Pt→Al Interaction: Fixation of CO2 and CS2, Activation of H2 and PhCONH2.
Authors: Devillard, Marc1,2, Declercq, Richard1,2, Nicolas, Emmanuel3, Ehlers, Andreas W.3, Backs, Jana4, Saffon-Merceron, Nathalie5, Bouhadir, Ghenwa1,2 bouhadir@chimie.ups-tlse.fr, Slootweg, J. Chris3 j.c.slootweg@vu.nl, Uhl, Werner4 uhlw@uni-muenster.de, Bourissou, Didier1,2 dbouriss@chimie.ups-tlse.fr
Source: Journal of the American Chemical Society. 4/13/2016, Vol. 138 Issue 14, p4917-4926. 10p.
Subjects: Chemical reactions, Ligands (Chemistry), Cyclic compounds, X-ray diffraction, Chemical structure
Abstract: Reaction of the geminal PAl ligand [Mes2PC(=CHPh)AltBu2] (1) with [Pt(PPh3)2(ethylene)] affords the T-shape Pt complex [(1)Pt(PPh3)] (2). X-ray diffraction analysis and DFT calculations reveal the presence of a significant Pt→Al interaction in 2, despite the strain associated with the four-membered cyclic structure. The Pt⋯Al distance is short [2.561(1) Å], the Al center is in a pyramidal environment [Σ(C-Al-C) = 346.6°], and the PCAl framework is strongly bent (98.3°). Release of the ring strain and formation of X→Al interactions (X = O, S, H) impart rich reactivity. Complex 2 reacts with CO2 to give the T-shape adduct 3 stabilized by an O→Al interaction, which is a rare example of a CO2 adduct of a group 10 metal and actually the first with η¹-CO2 coordination. Reaction of 2 with CS2 affords the crystalline complex 4, in which the PPtP framework is bent, the CS2 molecule is η²-coordinated to Pt, and one S atom interacts with Al. The Pt complex 2 also smoothly reacts with H2 and benzamide PhCONH2 via oxidative addition of H-H and H-N bonds, respectively. The ensuing complexes 5 and 7 are stabilized by Pt-H→Al and Pt-NH-C(Ph) = O→Al bridging interactions, resulting in 5- and 7-membered metallacycles, respectively. DFT calculations have been performed in parallel with the experimental work. In particular, the mechanism of reaction of 2 with H2 has been thoroughly analyzed, and the role of the Lewis acid moiety has been delineated. These results generalize the concept of constrained geometry TM→LA interactions and demonstrate the ability of Al-based ambiphilic ligands to participate in TM/LA cooperative reactivity. They extend the scope of small molecule substrates prone to such cooperative activation and contribute to improve our knowledge of the underlying factors. [ABSTRACT FROM AUTHOR]
Copyright of Journal of the American Chemical Society 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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DbLabel: Engineering Source
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  Data: A Significant but Constrained Geometry Pt→Al Interaction: Fixation of CO<subscript>2</subscript> and CS<subscript>2</subscript>, Activation of H<subscript>2</subscript> and PhCONH<subscript>2</subscript>.
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  Data: <searchLink fieldCode="AR" term="%22Devillard%2C+Marc%22">Devillard, Marc</searchLink><relatesTo>1,2</relatesTo><br /><searchLink fieldCode="AR" term="%22Declercq%2C+Richard%22">Declercq, Richard</searchLink><relatesTo>1,2</relatesTo><br /><searchLink fieldCode="AR" term="%22Nicolas%2C+Emmanuel%22">Nicolas, Emmanuel</searchLink><relatesTo>3</relatesTo><br /><searchLink fieldCode="AR" term="%22Ehlers%2C+Andreas+W%2E%22">Ehlers, Andreas W.</searchLink><relatesTo>3</relatesTo><br /><searchLink fieldCode="AR" term="%22Backs%2C+Jana%22">Backs, Jana</searchLink><relatesTo>4</relatesTo><br /><searchLink fieldCode="AR" term="%22Saffon-Merceron%2C+Nathalie%22">Saffon-Merceron, Nathalie</searchLink><relatesTo>5</relatesTo><br /><searchLink fieldCode="AR" term="%22Bouhadir%2C+Ghenwa%22">Bouhadir, Ghenwa</searchLink><relatesTo>1,2</relatesTo><i> bouhadir@chimie.ups-tlse.fr</i><br /><searchLink fieldCode="AR" term="%22Slootweg%2C+J%2E+Chris%22">Slootweg, J. Chris</searchLink><relatesTo>3</relatesTo><i> j.c.slootweg@vu.nl</i><br /><searchLink fieldCode="AR" term="%22Uhl%2C+Werner%22">Uhl, Werner</searchLink><relatesTo>4</relatesTo><i> uhlw@uni-muenster.de</i><br /><searchLink fieldCode="AR" term="%22Bourissou%2C+Didier%22">Bourissou, Didier</searchLink><relatesTo>1,2</relatesTo><i> dbouriss@chimie.ups-tlse.fr</i>
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  Data: <searchLink fieldCode="JN" term="%22Journal+of+the+American+Chemical+Society%22">Journal of the American Chemical Society</searchLink>. 4/13/2016, Vol. 138 Issue 14, p4917-4926. 10p.
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  Data: <searchLink fieldCode="DE" term="%22Chemical+reactions%22">Chemical reactions</searchLink><br /><searchLink fieldCode="DE" term="%22Ligands+%28Chemistry%29%22">Ligands (Chemistry)</searchLink><br /><searchLink fieldCode="DE" term="%22Cyclic+compounds%22">Cyclic compounds</searchLink><br /><searchLink fieldCode="DE" term="%22X-ray+diffraction%22">X-ray diffraction</searchLink><br /><searchLink fieldCode="DE" term="%22Chemical+structure%22">Chemical structure</searchLink>
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  Data: Reaction of the geminal PAl ligand [Mes2PC(=CHPh)AltBu2] (1) with [Pt(PPh3)2(ethylene)] affords the T-shape Pt complex [(1)Pt(PPh3)] (2). X-ray diffraction analysis and DFT calculations reveal the presence of a significant Pt→Al interaction in 2, despite the strain associated with the four-membered cyclic structure. The Pt⋯Al distance is short [2.561(1) Å], the Al center is in a pyramidal environment [Σ(C-Al-C) = 346.6°], and the PCAl framework is strongly bent (98.3°). Release of the ring strain and formation of X→Al interactions (X = O, S, H) impart rich reactivity. Complex 2 reacts with CO2 to give the T-shape adduct 3 stabilized by an O→Al interaction, which is a rare example of a CO2 adduct of a group 10 metal and actually the first with η¹-CO2 coordination. Reaction of 2 with CS2 affords the crystalline complex 4, in which the PPtP framework is bent, the CS2 molecule is η²-coordinated to Pt, and one S atom interacts with Al. The Pt complex 2 also smoothly reacts with H2 and benzamide PhCONH2 via oxidative addition of H-H and H-N bonds, respectively. The ensuing complexes 5 and 7 are stabilized by Pt-H→Al and Pt-NH-C(Ph) = O→Al bridging interactions, resulting in 5- and 7-membered metallacycles, respectively. DFT calculations have been performed in parallel with the experimental work. In particular, the mechanism of reaction of 2 with H2 has been thoroughly analyzed, and the role of the Lewis acid moiety has been delineated. These results generalize the concept of constrained geometry TM→LA interactions and demonstrate the ability of Al-based ambiphilic ligands to participate in TM/LA cooperative reactivity. They extend the scope of small molecule substrates prone to such cooperative activation and contribute to improve our knowledge of the underlying factors. [ABSTRACT FROM AUTHOR]
– Name: AbstractSuppliedCopyright
  Label:
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  Data: <i>Copyright of Journal of the American Chemical Society 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/jacs.6b01320
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        Text: English
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        PageCount: 10
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      – SubjectFull: Chemical reactions
        Type: general
      – SubjectFull: Ligands (Chemistry)
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      – SubjectFull: Cyclic compounds
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      – SubjectFull: X-ray diffraction
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      – SubjectFull: Chemical structure
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      – TitleFull: A Significant but Constrained Geometry Pt→Al Interaction: Fixation of CO2 and CS2, Activation of H2 and PhCONH2.
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              Text: 4/13/2016
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