Direct synthesis of diamine radical cations in crystalline form proceeding through oxidation of triphenylamine followed by the formation of a new C−N bond is reported. Although the oxidative coupling of triphenylamine is well studied, diamine products are rarely captured in their radical cation state. The neutral diamine most frequently obtained from this reaction pathway is N,N,N’,N’‐tetraphenylbenzidine. Herein, the capture of radical cations of diamines in crystalline form in one step starting with neutral triphenylamine was demonstrated, and the formation of two products (the radical cations of N,N,N′,N′‐tetraphenyl‐1,4‐benzenediamine or N,N,N′,N′‐tetraphenylbenzidine) depending on the oxidizing agent used was observed. The radical species are characterized by single‐crystal X‐Ray diffraction, electron paramagnetic resonance spectroscopy, and optical spectroscopy.
Computational Investigations of Enantioselection in Carbon–Carbon Bond Forming Reactions of Ruthenium Guanidinobenzimidazole Second Coordination Sphere Hydrogen Bond Donor Catalysts
- Award ID(s):
- 1664866
- NSF-PAR ID:
- 10252334
- Date Published:
- Journal Name:
- Organometallics
- Volume:
- 39
- Issue:
- 8
- ISSN:
- 0276-7333
- Page Range / eLocation ID:
- 1149 to 1162
- Format(s):
- Medium: X
- Sponsoring Org:
- National Science Foundation
More Like this
-
more » « less
Abstract -
Herein, the pyridinophanetetradentate ligand 3,6,9-trimethyl-3,6,9,15-tetraazabicyclo[9.3.1]pentadeca-1(15),11,13-triene, PyNMe 3 , is used to isolate and structurally characterize well-defined organometallic Ni( ii ) and Ni( iii ) complexes bearing the cycloneophyl fragment, an alkyl/aryl C-donor ligand. Furthermore, spectroscopic and cryo-mass spectrometry studies suggest the formation of a transient Ni( iv ) organometallic complex, and its relevance to C–C and C–O bond formation reactivity studies is discussed.more » « less
- Free Publicly Accessible Full Text
-
Accepted Manuscript1.0
- Journal Article:
- https://doi.org/10.1021/acs.organomet.0c00072
