Enhancing Diradical Character of Chichibabin's Hydrocarbon through Fluoride Substitution
Gargi Kundu1,2, Soumya Ranjan Dash2,3, Ravi Kumar2,3
1Inorganic Chemistry and Catalysis Division, CSIR-National Chemical Laboratory, Dr. Homi Bhabha Road Pashan, Pune, 411008, India.
Abstract:
In this work, 5-SIDipp [SIDipp=1,3-bis(2,6-diisopropylphenyl)-imidazolin-2-ylidene] (1) derived Chichibabin's hydrocarbon with an octafluorobiphenylene spacer (3) has been reported. The addition of two equivalents of 5-SIDipp with decafluorobiphenyl in presence of BF3 gives the double C-F bond activated imidazolium salt with two tetrafluoroborate anions, 2. Further reduction of 2 gives the fluorine substituted 5-SIDipp based Chichibabin's hydrocarbon, 3. Quantum chemical calculations suggested a singlet state of 3 with a singlet-triplet energy gap (ΔES-T ) of 3.7 kcal mol-1 , which is substantially lower with respect to the hydrogen substituted NHC-based Chichibabin's hydrocarbons (10.7 kcal mol-1 , B3LYP). As a result, the diradical character (y) of 3 (y=0.62) is also noticeably higher than the hydrogen substituted CHs (y=0.41-0.43). The ▵ES-T was found to be higher in CASSCF (22.24 kcal mol-1 ) and CASPT2 (11.17 kcal mol-1 ) for 3 and the diradical character (d) is 44.6 %.
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