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Abstract A new series of mono‐ and bis‐alkynyl CoIII(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 NAPMes(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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Rhenium Complexes with p‐Fluorophenylisocyanide
Abstract p‐Fluorophenylisocyanide (CNPhpF) reacts with [Re(CO)5Br] under stepwise exchange of the carbonyl ligands depending on the conditions applied. The reaction stops with the formation offac‐[Re(CO)3Br(CNPhpF)2] in boiling THF. An ongoing carbonyl exchange is observed at higher temperatures, e. g. in refluxing toluene, with the final formation of the [Re(CNPhpF)6]+cation. The progress of the reactions has been studied by19F NMR spectroscopy and the structures of [Re(CO)Br(CNPhpF)4] and [Re(CNPhpF)6](BPh4) have been elucidated by X‐ray diffraction.
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- Award ID(s):
- 1802646
- PAR ID:
- 10377316
- Publisher / Repository:
- Wiley Blackwell (John Wiley & Sons)
- Date Published:
- Journal Name:
- Zeitschrift für anorganische und allgemeine Chemie
- Volume:
- 649
- Issue:
- 1
- ISSN:
- 0044-2313
- Format(s):
- Medium: X
- Sponsoring Org:
- National Science Foundation
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