TY - JOUR
T1 - A Linear Two-Coordinate Cr(II) Complex
T2 - Synthesis, Characterization, and Reactivity
AU - Hsiao, Kai Chin
AU - Yang, Po Chun
AU - Fang, Chia Te
AU - Liu, Hsin Kuan
AU - Lin, Chun Yi
N1 - Publisher Copyright:
© 2023 Wiley-VCH GmbH.
PY - 2024/2/16
Y1 - 2024/2/16
N2 - The synthesis and characterization of a linear two-coordinate Cr(II) amido complex, Cr{N(tBu)Dipp}2 (Dipp=2,6-diisopropylphenyl), from the reaction of 1 molar equivalent (equiv) of CrCl2 and 2 equiv. of LiN(tBu)Dipp is reported. Single-crystal X-ray diffractometry (SC-XRD) analysis revealed that it has a short Cr−N bond distance of 1.8878(9) Å, which could be attributed to the relatively less bulky nature of the amido ligand compared with reported systems. Furthermore, the oxidation reaction of the two-coordinate Cr(II) complex was explored. The oxidation reaction of Cr{N(tBu)Dipp}2 with the one-electron oxidants AgOTf and [FeCp2][BArF4] (BArF4−=[B{C6H3−3,5-(CF3)2}4]−) afforded the trigonal planar three- and bent two-coordinate Cr(III) complexes Cr{N(tBu)Dipp}2(OTf) and [Cr{N(tBu)Dipp}2][BArF4], respectively. The reaction of Cr{N(tBu)Dipp}2 with 1 equiv. of the organic azides AdN3 (Ad=1-adamantyl) and PhN3 afforded the three-coordinate Cr(IV) imido complexes Cr{N(tBu)Dipp}2(NAd) and Cr{N(tBu)Dipp}2(NPh), respectively. The reaction of Cr{N(tBu)Dipp}2 and two equiv. of Me3NO afforded the Cr(VI) dioxo complex Cr{N(tBu)Dipp}2(O)2. The reaction of Cr{N(tBu)Dipp}2 with 1 equiv. of CyN=C=NCy resulted in the insertion of the carbodiimide into the Cr−N bond, with the formation of a three-coordinate Cr(II) complex. Finally, density functional theory (DFT) calculations were used to elucidate the electronic structure of these complexes.
AB - The synthesis and characterization of a linear two-coordinate Cr(II) amido complex, Cr{N(tBu)Dipp}2 (Dipp=2,6-diisopropylphenyl), from the reaction of 1 molar equivalent (equiv) of CrCl2 and 2 equiv. of LiN(tBu)Dipp is reported. Single-crystal X-ray diffractometry (SC-XRD) analysis revealed that it has a short Cr−N bond distance of 1.8878(9) Å, which could be attributed to the relatively less bulky nature of the amido ligand compared with reported systems. Furthermore, the oxidation reaction of the two-coordinate Cr(II) complex was explored. The oxidation reaction of Cr{N(tBu)Dipp}2 with the one-electron oxidants AgOTf and [FeCp2][BArF4] (BArF4−=[B{C6H3−3,5-(CF3)2}4]−) afforded the trigonal planar three- and bent two-coordinate Cr(III) complexes Cr{N(tBu)Dipp}2(OTf) and [Cr{N(tBu)Dipp}2][BArF4], respectively. The reaction of Cr{N(tBu)Dipp}2 with 1 equiv. of the organic azides AdN3 (Ad=1-adamantyl) and PhN3 afforded the three-coordinate Cr(IV) imido complexes Cr{N(tBu)Dipp}2(NAd) and Cr{N(tBu)Dipp}2(NPh), respectively. The reaction of Cr{N(tBu)Dipp}2 and two equiv. of Me3NO afforded the Cr(VI) dioxo complex Cr{N(tBu)Dipp}2(O)2. The reaction of Cr{N(tBu)Dipp}2 with 1 equiv. of CyN=C=NCy resulted in the insertion of the carbodiimide into the Cr−N bond, with the formation of a three-coordinate Cr(II) complex. Finally, density functional theory (DFT) calculations were used to elucidate the electronic structure of these complexes.
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U2 - 10.1002/asia.202300924
DO - 10.1002/asia.202300924
M3 - Article
C2 - 38059903
AN - SCOPUS:85184476133
SN - 1861-4728
VL - 19
JO - Chemistry - An Asian Journal
JF - Chemistry - An Asian Journal
IS - 4
M1 - e202300924
ER -