Synthesis, Characterization, and Reactivity of Tris(imido)chromium(VI) Complexes

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.
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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.