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Further Exploration of Aza-Cobalt-Cyclobutenes on Co ^III (TIM) Complexes: Reactivity and Spectroelectrochemistry

https://doi.org/10.1021/acs.organomet.2c00557

Rodriguez Segura, Leobardo; Clendening, Reese A.; Ren, Tong (October 2023, Organometallics)

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Formation of an Aza-Cobalt-Cyclobutene on Co III (TIM): Hidden Noninnocence of the TIM Ligand

https://doi.org/10.1021/acs.organomet.2c00117

Rodriguez Segura, Leobardo; Ren, Tong (May 2022, Organometallics)

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A Series of Mono- and Bis-Alkynyl Co(III) Complexes Supported by a Tetra-imine Macrocyclic Ligand (TIM)

https://doi.org/10.1021/acs.organomet.1c00423

Rodriguez Segura, Leobardo; Lee, Seul Ah; Mash, Brandon L.; Schuman, Ashley J.; Ren, Tong (October 2021, Organometallics)

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Further Studies of Co ^III (TIM) Mono‐Alkynyl and Bis‐Alkynyl Complexes

https://doi.org/10.1002/ejic.202200641

Rodriguez Segura, Leobardo; Cox, Kenneth E.; Samayoa‐Oviedo, Hugo Y.; Ren, Tong (December 2022, European Journal of Inorganic Chemistry)

Abstract A new series of mono‐ and bis‐alkynyl Co^III(TIM) complexes (TIM=2,3,9,10‐tetramethyl‐1,4,8,11‐tetraazacyclotetradeca‐1,3,8,10‐tetraene) is reported herein. Thetrans‐[Co(TIM)(C₂R)Cl]⁺complexes were prepared from the reaction betweentrans‐[Co(TIM)Cl₂]PF₆and HC₂R (R=tri(isopropyl)silyl or TIPS (1), ‐C₆H₄‐4‐^tBu (2), ‐C₆H₄‐4‐NO₂(3 a), andN‐mesityl‐1,8‐naphthalimide or NAP^Mes(4 a)) in the presence of Et₃N. The intermediate complexes of the typetrans‐[Co(TIM)(C₂R)(NCMe)](PF₆)(OTf),3 band4 b, were obtained by treating3 aand4 a, respectively, with AgOTf in CH₃CN. Furthermore, bis‐alkynyltrans‐[Co(TIM)(C₂R)₂]PF₆complexes,3 cand4 c, were generated following a second dehydrohalogenation reaction between3 band4 b, respectively, and the appropriate HC₂R in the presence of Et₃N. These new complexes have been characterized using X‐ray diffraction (2,3 a,4 a, and4 c), IR,¹H NMR, UV/Vis spectroscopy, fluorescent spectroscopy (4 c), and cyclic voltammetry.
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