Tris[(1-isopropylbenzimidazol-2-yl)dimethylsilyl]methyl metal complexes, [TismPri Benz ]M: a new class of metallacarbatranes, isomerization to a tris(N-heterocyclic carbene) derivative, and evidence for an inverted ligand field

Chemical Science
Serge RuccoloGerard Parkin

Abstract

The tris[(1-isopropylbenzimidazol-2-yl)dimethylsilyl]methyl ligand, [TismPriBenz], has been employed to form carbatrane compounds of both the main group metals and transition metals, namely [TismPriBenz]Li, [TismPriBenz]MgMe, [TismPriBenz]Cu and [TismPriBenz]NiBr. In addition to the formation of atranes, a zinc compound that exhibits κ3-coordination, namely [κ3-TismPriBenz]ZnMe, has also been obtained. Furthermore, the [TismPriBenz] ligand may undergo a thermally induced rearrangement to afford a novel tripodal tris(N-heterocyclic carbene) variant, as shown by the conversion of [TismPriBenz]Cu to [κ4-C4-TismPriBenz*]Cu. The transannular M-C bond lengths in the atrane compounds are 0.19-0.32 Å longer than the sum of the respective covalent radii, which is consistent with a bonding description that features a formally zwitterionic component. Interestingly, computational studies demonstrate that the Cu-Catrane interactions in [TismPriBenz]Cu and [κ4-C4-TismPriBenz*]Cu are characterized by an "inverted ligand field", in which the occupied antibonding orbitals are localized more on carbon than on copper.

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Citations

Jul 12, 2018·Chemistry : a European Journal·Christoph StuhlReiner Anwander
Sep 27, 2018·Dalton Transactions : an International Journal of Inorganic Chemistry·Zachary ThammavongsyJenny Y Yang
May 31, 2019·Dalton Transactions : an International Journal of Inorganic Chemistry·Patrick J QuinlivanGerard Parkin
Jun 18, 2019·Angewandte Chemie·Jelte S SteenJohannes E M N Klein
Mar 24, 2018·Chemical Science·Sriparna MukherjeeElena Jakubikova
Jun 28, 2018·Dalton Transactions : an International Journal of Inorganic Chemistry·Michael Rauch, Gerard Parkin
Jul 9, 2021·Journal of the American Chemical Society·Matthew HammondGerard Parkin
Nov 12, 2019·Journal of the American Chemical Society·Ida M DiMucciKyle M Lancaster
Dec 12, 2017·Journal of the American Chemical Society·Michael Rauch, Gerard Parkin
Dec 22, 2021·Dalton Transactions : an International Journal of Inorganic Chemistry·Gerard Parkin

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Methods Mentioned

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