@article {46910,
	title = {Transmetallation vs adduct: diverse reactivity of N,O-ketiminato germylene with [Cp*MCl2](2) (M = Rh or Ir; Cp* = eta(5)-C5Me5) and MCl5 (M = Nb and Ta)},
	journal = {Journal of Organometallic Chemistry},
	volume = {911},
	year = {2020},
	month = {APR },
	pages = {121142},
	type = {Article},
	abstract = {<p>The reactions of the germylenes, [(Dipp)NCMeCHCORGeCl] (1a: R = Me, 1b: R = Ph) with [Ir2Cl2(mu-Cl)(2)(eta(5)-Cp*)(2)] led to the formation of the adducts [(Dipp)NCMeCHCORGeClIrCl2Cp*] (3a: R = Me and 3b: R = Ph). On the other hand, [Rh2Cl2(mu-Cl)(2)(eta(5)-Cp*)(2)] does not react with the germylenes (1a and 1b). When the reactions of 1a and 1b are carried out with [Cp*TaCl4], the reaction led to decomposition. The reaction of 1a or 1b with TaCl5 yielded the transmetallated products [(Dipp)NCMeCHCORTaCl4] (4a: R = Me, 4b: R = Ph) with the extrusion of GeCl2. Our theoretical studies show that for, the insertion of TaCl5 to 1a and the formation of 4a with concomitant elimination of GeCl2 is energetically favourable. Extrusion of SnCl2 is also observed when the corresponding stannylene, [(Dipp)NCMeCHCOMeSnCl] was reacted with TaCl5. All these compounds have been characterized by H-1 and C-13 NMR spectroscopy, elemental analysis and the constitution of compounds 1b, 3b, and 4a were confirmed by single-crystal X-ray crystallography. (C) 2020 Elsevier B.V. All rights reserved.</p>
},
	keywords = {Adduct formation, Germylenes, Iridium, Ketoiminate, Tantalum, Transmetallation},
	issn = {0022-328X},
	doi = {10.1016/j.jorganchem.2020.121142},
	author = {Raghavendra, Beesam and Bakthavachalam, K. and Das, Tamal and Roisnel, Thierry and Sen, Sakya S. and Vanka, Kumar and Ghosh, Sundargopal}
}
@article {47901,
	title = {Hypersilyl substituent in heavier low-valent group 14 chemistry},
	journal = {European Journal of Inorganic Chemistry},
	volume = {2022},
	year = {2022},
	month = {APR },
	pages = {e202200071},
	type = {Review},
	abstract = {<p>
	The isolation of unusual compounds with low-valent main-group elements would not have been possible without the development of a series of sterically demanding ligands with bulky substituents. While early literature recognizes the advent of the sterically demanding tris(trimethylsilyl)silyl (SiMe3)(3)Si- group, also known as hypersilyl group, to stabilize species with new coordination modes for the main group elements, it has largely been more recent studies that have utilized this group for isolating stable compounds with low-valent main-group elements. Such compounds are not only interesting from the structure-bonding point of view but showcase potential for small molecule activation under ambient conditions. This review will cover the recent developments in stabilizing unusual compounds with group 14 elements using the exceptionally strong sigma-donor properties and pronounced steric effects of the hypersilyl moiety, emphasizing their synthesis, structure, and reactivity.</p>
},
	keywords = {Germylenes, Hydroboration, Hypersilyl, silylenes, Stannylenes},
	issn = {1434-1948},
	doi = {10.1002/ejic.202200071},
	author = {Gour, Kritika and Bisai, Milan Kumar and Sen, Sakya S.}
}
