<?xml version="1.0" encoding="UTF-8"?><xml><records><record><source-app name="Biblio" version="7.x">Drupal-Biblio</source-app><ref-type>17</ref-type><contributors><authors><author><style face="normal" font="default" size="100%">Kundu, Gargi</style></author><author><style face="normal" font="default" size="100%">Dash, Soumya Ranjan</style></author><author><style face="normal" font="default" size="100%">Kumar, Ravi</style></author><author><style face="normal" font="default" size="100%">Vanka, Kumar</style></author><author><style face="normal" font="default" size="100%">Ghosh, Aryya</style></author><author><style face="normal" font="default" size="100%">Sen, Sakya S.</style></author></authors></contributors><titles><title><style face="normal" font="default" size="100%">Enhancing diradical character of chichibabin's hydrocarbon through fluoride substitution</style></title><secondary-title><style face="normal" font="default" size="100%">ChemPlusChem</style></secondary-title></titles><keywords><keyword><style  face="normal" font="default" size="100%">C-F Bond Activation</style></keyword><keyword><style  face="normal" font="default" size="100%">Chichibabin &amp; PRIME</style></keyword><keyword><style  face="normal" font="default" size="100%">DFT</style></keyword><keyword><style  face="normal" font="default" size="100%">N-Heterocyclic carbene</style></keyword><keyword><style  face="normal" font="default" size="100%">s Hydrocarbon</style></keyword></keywords><dates><year><style  face="normal" font="default" size="100%">2023</style></year><pub-dates><date><style  face="normal" font="default" size="100%">AUG</style></date></pub-dates></dates><volume><style face="normal" font="default" size="100%">88</style></volume><pages><style face="normal" font="default" size="100%">e202300273</style></pages><language><style face="normal" font="default" size="100%">eng</style></language><abstract><style face="normal" font="default" size="100%">&lt;p&gt;
	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 (?ES-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 %.&lt;/p&gt;
</style></abstract><issue><style face="normal" font="default" size="100%">8</style></issue><work-type><style face="normal" font="default" size="100%">Article</style></work-type><custom3><style face="normal" font="default" size="100%">&lt;p&gt;
	Foreign&lt;/p&gt;
</style></custom3><custom4><style face="normal" font="default" size="100%">&lt;p&gt;
	3.4&lt;/p&gt;
</style></custom4></record><record><source-app name="Biblio" version="7.x">Drupal-Biblio</source-app><ref-type>17</ref-type><contributors><authors><author><style face="normal" font="default" size="100%">Kundu, Gargi</style></author><author><style face="normal" font="default" size="100%">Amrutha, P. R.</style></author><author><style face="normal" font="default" size="100%">Tothadi, Srinu</style></author><author><style face="normal" font="default" size="100%">Sen, Sakya S.</style></author></authors></contributors><titles><title><style face="normal" font="default" size="100%">Access to NHC-Boryl mono- and bis-selenide and utility as mild selenium transfer reagent including to the C-F bond</style></title><secondary-title><style face="normal" font="default" size="100%">Chemistry- a european journal</style></secondary-title></titles><keywords><keyword><style  face="normal" font="default" size="100%">boron</style></keyword><keyword><style  face="normal" font="default" size="100%">C-F Bond Activation</style></keyword><keyword><style  face="normal" font="default" size="100%">N-Heterocyclic carbene</style></keyword><keyword><style  face="normal" font="default" size="100%">Ring expansion</style></keyword><keyword><style  face="normal" font="default" size="100%">Selenium</style></keyword></keywords><dates><year><style  face="normal" font="default" size="100%">2024</style></year><pub-dates><date><style  face="normal" font="default" size="100%">JAN </style></date></pub-dates></dates><volume><style face="normal" font="default" size="100%">30</style></volume><language><style face="normal" font="default" size="100%">eng</style></language><abstract><style face="normal" font="default" size="100%">&lt;p&gt;
	Reactions of 5-SIDipp &amp;amp; sdot; BH3 (5-SIDipp=1,3-bis(2,6-diisopropylphenyl)-imidazolin-2-ylidene) (1) with diphenyldiselenide provide access to 5-SIDipp-boryl mono- (5-SIDipp &amp;amp; sdot; BH2SePh) (2) and bis-selenide (5-SIDipp &amp;amp; sdot; BH(SePh)2) (3). The facile cleavage of the B-Se bond makes 2 a neutral source of selenium nucleophiles in substitutions reactions with benzyl bromides, and provide access to the corresponding selenoethers. The direct transformations of one of the C(sp2)-F bonds of C5F5N and C6F5CF3 to C-Se bonds have also been achieved by the use of 2 without employing transition-metal catalysts. While it was previously established that C6F6 could undergo complete defluoroselenation under harsh conditions, we successfully achieved partial defluorination of C6F6 by employing 2 as a mild selenide transfer reagent. During the formation of C-Se bonds through the cleavage of C-F bonds, the potential by-product NHC &amp;amp; sdot; BH2F undergoes ring expansion of the NHC, leading to the formation of the six-membered diaazafluoroborinane (7). Access to NHC &amp;amp; sdot; boryl mono- and bis-selenides from NHC &amp;amp; sdot; BH3 has been achieved. The boryl mono selenide has been demonstrated to function as a selenium transfer reagent, enabling the synthesis of selenoethers from benzyl bromide. Additionally, it can also facilitate the conversion of the challenging aromatic C-F bond to a C-Se bond, resulting in concomitant ring expansion of NHC &amp;amp; sdot; haloborane.image&lt;/p&gt;
</style></abstract><issue><style face="normal" font="default" size="100%">6</style></issue><work-type><style face="normal" font="default" size="100%">Article</style></work-type><custom3><style face="normal" font="default" size="100%">&lt;p&gt;
	Foreign&lt;/p&gt;
</style></custom3><custom4><style face="normal" font="default" size="100%">&lt;p&gt;
	4.3&lt;/p&gt;
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