01429nas a2200289 4500008004100000022001400041245008100055210006300136260000800199490000700207520052100214653002200735653001300757653003100770653001700801653001200818653002800830653002300858653002600881653002500907653002900932100002600961700002000987700001501007700001901022856009801041 2017 eng d a1359-734500aC(sp(3))-F, C(sp(2))-F and C(sp(3))-H bond activation at silicon(II) centers0 aCsp3F Csp2F and Csp3H bond activation at siliconII centers cSEP0 v533 a

Silylene [PhC(NtBu)(2)SiN(SiMe3)(2)] (1) cleaves the C(sp(3))-H and C-F bonds of acetophenone and 1,1,1-trifluoroacetophenone, respectively, under mild conditions. The reaction is initiated via a nucleophilic attack from the oxygen to the silicon atom followed by C-F/H bond cleavage. The scope of C-F bond activation has further been extended with C6F6 and C6F5CF3.

10aBoron triple bond10aC-F Bond10aFluorinated Building-Block10aH Activation10aKetones10aN-heterocyclic carbenes10aOxodative Addition10aPerfluorinated Arenes10aSelective Activation10aTransition-Metal Centers1 aSwamy, V., S. V. S. N1 aParvin, Nasrina1 aRaj, Vipin1 aSen, Sakya, S. uhttps://library.ncl.res.in/content/csp3-f-csp2-f-and-csp3-h-bond-activation-siliconii-centers01241nas a2200181 4500008004100000245008400041210006900125260000800194300001400202490000700216520062600223100002000849700002300869700001400892700001900906700001800925856011600943 2017 eng d00aStrikingly diverse reactivity of structurally identical silylene and stannylene0 aStrikingly diverse reactivity of structurally identical silylene cMAY a6528-65320 v463 aThe reactivity of structurally identical silylene and stannylene [PhC(NtBu)(2)EN(SiMe3)(2)] (E = Si (1) and Sn (2)) towards coinage metals has been explored. While 1 has the propensity to form an adduct with coinage metals (4 and 5), 2 undergoes a ligand exchange reaction with copper halides and silver triflate leading to PhC(NtBu) 2SnX (X = Br (6), Cl (7), and OSO2CF3 (8)) with concomitant formation of [M{N(SiMe3) (2)}] (M = Cu, Ag). However, with AgSbF6 both 1 and 2 led to ion pairs, 9(+) .SbF(6)(-)and 10(+) . SbF(6)(-)displaying weaker Ag center dot center dot center dot center dot F interactions in the latter.1 aParvin, Nasrina1 aDasgupta, Rajarshi1 aPal, Shiv1 aSen, Sakya, S.1 aKhan, Shabana uhttps://library.ncl.res.in/content/strikingly-diverse-reactivity-structurally-identical-silylene-and-stannylene00884nas a2200205 4500008004100000022001400041245008500055210006900140260000800209300001400217490000700231520019300238100002000431700001900451700002900470700001900499700002700518700001800545856011500563 2021 eng d a1359-734500aDiverse reactivity of NOBF4 towards silylene, disilene, germylene and stannylene0 aDiverse reactivity of NOBF4 towards silylene disilene germylene  cMAY a5008-50110 v573 a

{The reactivity of NOBF4 towards silylene, disilene, germylene, stannylenes has been described. Smooth syntheses of compounds of composition [PhC(NtBu)(2)E(= O -> BF3)N(SiMe3)(2)

1 aParvin, Nasrina1 aSen, Nilanjana1 aMuhasina, Puthan, Veetil1 aTothadi, Srinu1 aParameswaran, Pattiyil1 aKhan, Shabana uhttps://library.ncl.res.in/content/diverse-reactivity-nobf4-towards-silylene-disilene-germylene-and-stannylene01757nas a2200181 4500008004100000022001400041245010100055210006900156260000900225300001400234490000700248520113700255100001901392700002001411700001901431700001801450856010701468 2021 eng d a0276-733300aReactivity of (TMS)(2)N(eta(1)-Cp*)Si=Si(eta(1)-Cp*)N(TMS)(2) toward the Halides of Groups 13-150 aReactivity of TMS2Neta1CpSiSieta1CpNTMS2 toward the Halides of G cJUN  a1874-18830 v403 aIn this paper, we have demonstrated the unique reactivity of a previously reported disilene [(TMS)(2)N(eta(1)-Me5C5)Si=Si(eta(1)-Me5C5)N(TMS)(2)] (1) with the halides of groups 13-15, which resulted in the formation of silicon-E (E = B, Al, Ge, P) bonds. Treatment of 1 with Lewis acidic BCl3 led to the formation of a cationic boron species [Cp*BSi(Cl)(2)N(TMS)(2))][BCl3SiCl3] (2). In contrast, the reaction of 1 with BCy2Cl afforded an oxidative addition product [(TMS)(2)N(eta(1)-Me5C5)Si(BCy2)(Cl)] (3) via the insertion of a Si(II) atom into the B-Cl bond. Extending the reaction with its higher congener led to classical Lewis acid-base adducts, (TMS)(2)N(eta(1)-Me5C5)Si -> AlCl3 (4) and (TMS)(2)N(eta(1)-Me5C5)Si -> AlBr3 (5), respectively. The reaction of GeCl2 with 1 proceeded in a completely different manner and resulted in a hybrid dendrimeric compound [HGe(Si(Cl)(2)N(TMS)(2))(3)] (6), whereas, with SnCl2, it led to Cp*SnCl (7). Lastly, the reaction of Ph2PCl followed the same pattern like Cy2BCl and led to the formation of an oxidative addition product [(TMS)(2)N(eta(1)-Me5C5)Si(PPh2)(Cl)] (9) with a Si-P bond.1 aSen, Nilanjana1 aParvin, Nasrina1 aTothadi, Srinu1 aKhan, Shabana uhttps://library.ncl.res.in/content/reactivity-tms2neta1-cpsisieta1-cpntms2-toward-halides-groups-13-1501160nas a2200205 4500008004100000022001400041245009900055210006900154260000900223300001400232490000700246520044700253100002000700700001900720700001900739700002200758700002700780700001800807856012900825 2021 eng d a0276-733300aSynthesis and application of silylene-stabilized low-coordinate Ag(I)-arene cationic complexes0 aSynthesis and application of silylenestabilized lowcoordinate Ag cJUN  a1626-16320 v403 aWe report the first examples of N-heterocyclic silylene-stabilized monocoordinate Ag(I) cationic complexes weakly bound to the free arene rings (C6H6, C6Me6, and C7H8). Further, the application of these electrophilic Ag(I) complexes as catalysts has been investigated toward A(3)-coupling reactions, which afforded a series of propargylamines in good to excellent yields with low catalyst loading under a solvent-free condition (19 examples).1 aParvin, Nasrina1 aSen, Nilanjana1 aTothadi, Srinu1 aMuhammed, Shahila1 aParameswaran, Pattiyil1 aKhan, Shabana uhttps://library.ncl.res.in/content/synthesis-and-application-silylene-stabilized-low-coordinate-agi-arene-cationic-complexes01202nas a2200181 4500008004100000022001400041245010700055210006900162260000900231300001400240490000700254520054100261100002500802700002000827700002400847700001800871856013100889 2024 eng d a1359-734500aHybrid silylene-Pd catalyst: efficient C-N cross-coupling of sterically bulky amines and chiral amines0 aHybrid silylenePd catalyst efficient CN crosscoupling of sterica cSEP  a9958-99610 v603 a

Herein, we report a catalytic system with N-heterocyclic silylene (NHSi)-phosphine-based hybrid bidentate ligands [PhC(NtBu)2SiN(PR2)(2,6-iPr2-C6H3)] and Pd(dba)2, which serves as an effective catalyst for C-N cross-coupling of a wide range of sterically bulky amines and optically active amines, which is challenging otherwise. Herein, we report a hybrid silylene-based bidentate ligand (SiNP)-Pd(0) catalytic system, which performs the C-N coupling of difficult substrates, e.g., sterically bulky amines and chiral amines.

1 aKaulage, Sandeep, H.1 aParvin, Nasrina1 aKhopade, Kishor, V.1 aKhan, Shabana uhttps://library.ncl.res.in/content/hybrid-silylene-pd-catalyst-efficient-c-n-cross-coupling-sterically-bulky-amines-and-chiral