@article {46716,
	title = {Amidinato germylene-zinc complexes: synthesis, bonding, and reactivity},
	journal = {Chemistry-An Asian Journal},
	volume = {15},
	year = {2020},
	month = {OCT },
	pages = {3116-3121},
	type = {Article},
	abstract = {<p>Despite the explosive growth of germylene compounds as ligands in transition metal complexes, there is a modicum of precedence for the germylene zinc complexes. In this work, the synthesis and characterization of new germylene zinc complexes [PhC(NtBu)(2)Ge{N(SiMe3)(2)}-\&gt; ZnX2](2)(X= Br (2) and I (3)) supported by (benz)-amidinato germylene ligands are reported. The solid-state structures of2and3have been validated by single-crystal X-ray diffraction studies, which revealed the dimeric nature of the complexes, with distorted tetrahedral geometries around the Ge and Zn center. DFT calculations reveal that the Ge-Zn bonds in2and3are dative in nature. The reaction of2with elemental sulfur resulted in the first structurally characterized germathione stabilized ZnBr(2)complexes PhC(NtBu)(2)Ge(=S){N(SiMe3)(2)}-\&gt; ZnBr2(5). Therefore, the Ge=S in5is in-between Ge-S single and Ge=S double bond length, owing to the coordination of a sulfur lone pair of electrons to ZnBr2.</p>
},
	keywords = {DFT, Germathione, Germylene, X-ray Structure, zinc},
	issn = {1861-4728},
	doi = {10.1002/asia.202000807, Early Access Date = SEP 2020},
	author = {Yadav, Sandeep and Kumar, Rohit and Raj, K. Vipin and Yadav, Prashant and Vanka, Kumar and Sen, Sakya S.}
}
@article {47654,
	title = {Unsymmetrical sp(2)-sp(3) disilenes},
	journal = {Angewandte Chemie-International Edition},
	volume = {60},
	year = {2021},
	month = {SEP },
	pages = {20706-20710},
	type = {Article},
	abstract = {Disilenes with differently coordinated silicon atoms are not known. Here, we have shown the high yield synthesis of a range of disilenes (2-4 and 6) upon reaction of a hypersilyl silylene PhC(NtBu)(2)SiSi(SiMe3)(3) (1) with aliphatic chlorophosphines. The most striking characteristic of these disilenes is the presence of two differently coordinated Si atoms (one is three-coordinated, the other four-coordinated). The analogous reaction with Ph2PCl did not afford the desired disilene, but, surprisingly, led to the first tetraphosphinosilane (8). DFT calculations were performed to understand the bonding in disilenes and differences in reactivity of the complexes.},
	keywords = {chlorophosphine, DFT, disilene, hypersilylsilylene},
	issn = {1433-7851},
	doi = {10.1002/anie.202107847},
	author = {Bisai, Milan Kumar and Das, Tamal and Vanka, Kumar and Gonnade, Rajesh G. and Sen, Sakya S.}
}
@article {48755,
	title = {Enhancing diradical character of chichibabin{\textquoteright}s hydrocarbon through fluoride substitution},
	journal = {ChemPlusChem},
	volume = {88},
	year = {2023},
	month = {AUG},
	pages = {e202300273},
	type = {Article},
	abstract = {<p>
	In this work, 5-SIDipp [SIDipp=1,3-bis(2,6-diisopropylphenyl)-imidazolin-2-ylidene] (1) derived Chichibabin{\textquoteright}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{\textquoteright}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{\textquoteright}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 \%.</p>
},
	keywords = {C-F Bond Activation, Chichibabin \& PRIME, DFT, N-Heterocyclic carbene, s Hydrocarbon},
	issn = {2192-6506},
	doi = {10.1002/cplu.202300273},
	author = {Kundu, Gargi and Dash, Soumya Ranjan and Kumar, Ravi and Vanka, Kumar and Ghosh, Aryya and Sen, Sakya S.}
}
