Unusual Electronic Structures of an Electron Transfer Series of [Cr(µ-η1 : η1 -N2 )Cr]0/1+/2.
Angew Chem Int Ed Engl
; 63(13): e202315386, 2024 Mar 22.
Article
em En
| MEDLINE
| ID: mdl-38299757
ABSTRACT
In dinitrogen (N2 ) fixation chemistry, bimetallic end-on bridging N2 complexes M(µ-η1 η1 -N2 )M can split N2 into terminal nitrides and hence attract great attention. To date, only 4d and 5d transition complexes, but none of 3d counterparts, could realize such a transformation. Likewise, complexes {[Cp*Cr(dmpe)]2 (µ-N2 )}0/1+/2+ (1-3) are incapable to cleave N2 , in contrast to their Mo congeners. Remarkably, cross this series the N-N bond length of the N2 ligand and the N-N stretching frequency exhibit unprecedented nonmonotonic variations, and complexes 1 and 2 in both solid and solution states display rare thermally activated ligand-mediated two-center spin transitions, distinct from discrete dinuclear spin crossovers. In-depth analyses using wave function based ab initio calculations reveal that the Cr-N2 -Cr bonding in complexesâ
1-3 is distinguished by strong multireference character and cannot be described by solely one electron configuration or Lewis structure, and that all intriguing spectroscopic observations originate in their sophisticate multireference electronic structures. More critical is that such multireference bonding of complexesâ
1-3 is at least a key factor that contributes to their kinetic inertness toward N2 splitting. The mechanistic understanding is then used to rationalize the disparate reactivity of related 3d M(µ-η1 η1 -N2 )M complexes compared to their 4d and 5d analogs.
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MEDLINE
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En
Ano de publicação:
2024
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Article