@article {44204,
	title = {Beyond hydrofunctionalisation: a well-defined calcium compound catalysed mild and efficient carbonyl cyanosilylation},
	journal = {Chemistry-A European Journal},
	volume = {24},
	year = {2018},
	month = {JAN},
	pages = {1269-1273},
	type = {Article},
	abstract = {<p>Organocalcium compounds have been reported as efficient catalysts for various transformations, for cases in which one of the substrates contained an E-H (E=B, N, Si, P) bond. Here, we look at the possibility of employing an organocalcium compound for a transformation in which none of the precursors has a polar E-H bond. This study demonstrates the utilization of a well-defined amidinatocalcium iodide, [PhC(NiPr)(2)CaI] (1) for cyanosilylation of a variety of aldehydes and ketones with Me3SiCN under ambient conditions without the need of any co-catalyst. The reaction mechanism involves a weak adduct formation between 1 and Me3SiCN leading to the activation of the Si-C bond, which subsequently undergoes sigma-bond metathesis with a C=O moiety. Such a mechanistic pathway is unprecedented in alkaline earth metal chemistry. Experimental and computational studies support the mechanism.</p>},
	keywords = {Ca catalysis, carbonyls, cyanosilylation, Density functional calculations, transition-metal free},
	issn = {0947-6539},
	doi = {10.1002/chem.201705795},
	author = {Yadav, Sandeep and Dixit, Ruchi and Vanka, Kumar and Sen, Sakya S.}
}
@article {46425,
	title = {Saturated N-heterocyclic carbene based thiele{\textquoteright}s hydrocarbon with a tetrafluorophenylene linker},
	journal = {Chemistry-A European Journal},
	year = {2019},
	month = {NOV},
	type = {Article; Early Access},
	abstract = {<p>The synthesis of a SIPr [1,3-bis(2,6-diisopropylphenyl)-imidazolin-2-ylidene] derived Kekule diradicaloid with a tetrafluorophenylene spacer (3) has been described. Two synthetic routes have been reported to access 3. The cleavage of C-F bond of C6F6 by SIPr in the presence of BF3 led to double C-F activated compound with two tetrafluoro borate counter anions (2), which upon reduction by lithium metal afforded 3. Alternatively, 3 can be directly accessed in one step by reacting SIPr with C6F6 in presence of Mg metal. Compounds 2 and 3 were well characterized spectroscopically and by single-crystal X-ray diffraction studies. Experimental and computational studies support the cumulenic closed-shell singlet state of 3 with a singlet-triplet energy gap (Delta ES-T) of 23.7 kcal mol(-1).</p>
},
	keywords = {C-F activation, Density functional calculations, fluorine, Kekule diradicaloids, saturated NHC},
	issn = {0947-6539},
	doi = {10.1002/chem.201904421},
	author = {Kundu, Gargi and De, Sriman and Tothadi, Srinu and Das, Abhishek and Koley, Debasis and Sen, Sakya S.}
}
