期刊
INORGANIC CHEMISTRY
卷 60, 期 9, 页码 6115-6124出版社
AMER CHEMICAL SOC
DOI: 10.1021/acs.inorgchem.0c03778
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资金
- U.S. National Science Foundation [CHE-1954254]
- National Science Foundation Graduate Research Fellowship [DGE1752134]
- URB-CNRS
The study reports a new type of N-2-bridged rhenium (III) complex in which N-2 binding occurs at a higher oxidation level. Computational studies show that the weakly pi-donor pincer ligand stabilizes an open-shell electronic configuration, leading to enhanced N-2 binding in the bridged complex. The SQUID magnetometry analysis confirms a singlet ground state for this complex and offers explanations for the antiferromagnetic coupling observed.
Bimetallic nitrogen (N-2) splitting to form metal nitrides is an attractive method for N-2 fixation. Although a growing number of pincer-supported systems can bind and split N-2, the precise relationship between the ligand properties and N-2 binding/ splitting remains elusive. Here we report the first example of an N-2-bridged rhenium(III) complex, [(trans-P(2)(tBu)Pyrr)ReCl2](2)(mu-eta(1):eta(1)-N-2) (P-2 (tBu)Pyrr = [2,5-((CH2PBu2)-Bu-t)(2)C4H2N](-)). In this case, N-2 binding occurs at a higher oxidation level than that in other reported pincer analogues. Analysis of the electronic structure through computational studies shows that the weakly pi-donor pincer ligand stabilizes an open-shell electronic configuration that leads to enhanced binding of N-2 in the bridged complex. Utilizing SQUID magnetometry, we demonstrate a singlet ground state for this Re-N-N-Re complex, and we offer tentative explanations for antiferromagnetic coupling of the two local S = 1 sites. Reduction and subsequent heating of the rhenium(III)-dinitrogen complex leads to chloride loss and cleavage of the N-N bond with isolation of the terminal rhenium(V) nitride complex (P(2)(tBu)Pyrr)ReNCl.
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