Synthesis, Characterization, and Reactivity of Tris(imido)chromium(VI) Complexes
| Author(s) | Wu, Pengcheng | |
| Author(s) | Yap, Glenn P. A. | |
| Author(s) | Theopold, Klaus H. | |
| Date Accessioned | 2024-02-12T19:30:58Z | |
| Date Available | 2024-02-12T19:30:58Z | |
| Publication Date | 2023-11-27 | |
| Description | This document is the Accepted Manuscript version of a Published Work that appeared in final form in Inorganic Chemistry, copyright © 2023 American Chemical Society after peer review and technical editing by the publisher. To access the final edited and published work see https://doi.org/10.1021/acs.inorgchem.3c03169. This article will be embargoed until 11/27/2024. | |
| Abstract | Multiple tris(imido)chromium(VI) complexes, including neutral and ionic compounds, have been synthesized and characterized. (tBuN)2Cr(NHtBu)Cl can be deprotonated by KN(SiMe3)2, yielding K[(tBuN)3CrCl]. This tris(imido) anion undergoes nucleophilic substitution by PPh3 and tBuNH2 to form (tBuN)3Cr(PPh3) and (tBuN)2Cr(NHtBu)2, respectively. (tBuN)2Cr(NHtBu)2 loses one amido proton to form K[(tBuN)3Cr(NHtBu)] upon reaction with KN(SiMe3)2. The imido ligands of K[(tBuN)3CrCl] and (tBuN)3Cr(PPh3) are attacked by the electrophile MeI to produce (tBuN)2Cr(NMetBu)Cl and (tBuN)2Cr(NMetBu)I, respectively. An alternate way to make tris(imido) anions is deprotonation of (tBuN)2Cr(NHtBu)Cl by an alkyl lithium reagent, e.g., Me3SiCH2Li. The resulting Li[(tBuN)3CrCl] was alkylated by a second equivalent of Me3SiCH2Li to form Li[(tBuN)3Cr(CH2SiMe3)]. Reactivity studies of tris(imido) complexes show cycloaddition with PhNCO or CO2 to form metallacycles. | |
| Sponsor | We gratefully acknowledge NSF (CHE-1565955) and the University of Delaware for partial support of this work. Support for shared instrumentation was provided by the NSF (CHE-1048367 and CHE-0840401) and NIH (P20GM104316, P30GM110758, S10RR026962-0, and S10-OD026896A). | |
| Citation | Wu, Pengcheng, Glenn P. A. Yap, and Klaus H. Theopold. “Synthesis, Characterization, and Reactivity of Tris(Imido)Chromium(VI) Complexes.” Inorganic Chemistry 62, no. 47 (November 27, 2023): 19332–40. https://doi.org/10.1021/acs.inorgchem.3c03169. | |
| ISSN | 1520-510X | |
| URL | https://udspace.udel.edu/handle/19716/33973 | |
| Language | en_US | |
| Publisher | Inorganic Chemistry | |
| Title | Synthesis, Characterization, and Reactivity of Tris(imido)chromium(VI) Complexes | |
| Type | Article |
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