02271nas a2200181 4500008004100000022001400041245007900055210006900134260011000203300001600313490000700329520156600336100002601902700001401928700001801942700001901960856011001979 2015 eng d a1477-922600aCations and dications of heavier group 14 elements in low oxidation states0 aCations and dications of heavier group 14 elements in low oxidat aTHOMAS GRAHAM HOUSE, SCIENCE PARK, MILTON RD, CAMBRIDGE CB4 0WF, CAMBS, ENGLANDbROYAL SOC CHEMISTRYcJUN a12903-129230 v443 a

Cations and dications of heavier group 14 elements in their low oxidation state have received widespread attention in recent years. The journey started with the isolation of a series of cations of the composition [(C5Me5)E:](+) [E = Si-Pb], followed by the more recent isolation of a Ge(II) dication encapsulated within a cryptand, a carbodiphosphorane stabilized [GeCl](+) monocation with a two coordinate Ge atom, Si(II) cations and dications stabilized by N-heterocyclic carbenes (NHCs), which highlights the ongoing growth and interest in the chemistry of tetrel(II) cations. This is presumably because the central atom (E) in these compounds contains two or three unoccupied valence orbitals as well as holds a lone pair of electrons. Such an electronic description represents ambiphilicity, which is of great interest for catalysis. The successful synthesis of divalent group 14 cations requires new synthetic strategies based on the sterically demanding neutral or monoanionic ligands, utilization of counter anions, and solvents with low nucleophilicity in order to minimize the degree of interactions with the cations. An alternative approach for the realization of divalent cations of group 14 elements is their coordination to the transition metals. This synthetic approach was successfully applied for the isolation of a range of transition metal coordinated divalent cations of group 14 elements. Apart from arousing academic interest some of these cations have found application as activators in the Ziegler-Natta polymerization of alkenes.

1 aSwamy, V., S. V. S. N1 aPal, Shiv1 aKhan, Shabana1 aSen, Sakya, S. uhttps://library.ncl.res.in/content/cations-and-dications-heavier-group-14-elements-low-oxidation-states-001241nas 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-stannylene01423nas a2200193 4500008004100000022001400041245008200055210006900137260000900206300001600215490000700231520078600238100002101024700002201045700001901067700001501086700001801101856011001119 2020 eng d a0020-166900aBis(silanetellurone) with C-H center dot center dot center dot Te Interaction0 aBissilanetellurone with CH center dot center dot center dot Te I cDEC  a17811-178210 v593 a

Herein, we report the synthesis of a series of bis(silanechalcogenones) [Ch = Te (2), S (3), or Se (4)] using an N-heterocyclic silylene-based SiCSi pincer ligand (1). 2 is the first example of a bis(silanetellurone) derivative. The bonding patterns of 2-4 were extensively studied by natural bond orbital, quantum theory of atoms in molecules, and noncovalent interaction index analyses, and these exhibit weak C-H center dot center dot center dot Ch interaction. The analogous reaction of 1 with trimethyl N-oxide produced a novel bis(cyclosiloxane) derivative (5). All of the complexes are duly characterized by single-crystal X-ray diffraction studies, multinuclear nuclear magnetic resonance (H-1, C-13, and Si-29) spectroscopy, and high-resolution mass spectrometry.

1 aGhosh, Moushakhi1 aPanwaria, Prakash1 aTothadi, Srinu1 aDas, Aloke1 aKhan, Shabana uhttps://library.ncl.res.in/content/bissilanetellurone-c-h-center-dot-center-dot-center-dot-te-interaction01526nas a2200169 4500008004100000022001400041245011200055210006900167260000800236300001400244490000700258520090100265100002101166700001901187700001801206856013201224 2021 eng d a0276-733300aCarbazole substituted amidinato silylene: synthesis, bonding, and coordination behavior with coinage metals0 aCarbazole substituted amidinato silylene synthesis bonding and c cSEP a3201-32100 v403 aIn this work, the synthesis and characterization of a new carbazole substituted amidinatosilylene (1) and its coinage metal complexes 3-8 are being reported. Before the complexation reactions, we prepared [PhC(N+Bu)(2)Si(Cbz)-> Co(CO)Cp] complex (2) to estimate the sigma-donating strength of the newly synthesized silylene 1. Further, several commonly available coinage metal salts were utilized for the complexation reactions with 1, which afforded complexes 3-8. The solid-state structures of 1-8 have been validated by single-crystal X-ray diffraction studies, NMR spectroscopy, and mass spectroscopy. DFT studies were also performed to understand the bonding scenario of 1 and 3-7. Of note, 1 consists of a HOMO on its carbazolide moiety, and the HOMO-1 features the silylene character. We also compared the HOMO-LUMO gap of 1 with other amidinato silylenes having different N-substitutions.1 aGhosh, Moushakhi1 aTothadi, Srinu1 aKhan, Shabana uhttps://library.ncl.res.in/content/carbazole-substituted-amidinato-silylene-synthesis-bonding-and-coordination-behavior-coinage00884nas 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-complexes01928nas a2200229 4500008004100000022001400041245008600055210006900141260000800210300001600218490000700234520116200241100002001403700002501423700002301448700001901471700002701490700002701517700002101544700001801565856011501583 2022 eng d a0020-166900aFirst-row transition metal complexes of a phosphine-silylene- based hybrid ligand0 aFirstrow transition metal complexes of a phosphinesilylene based cAUG a13330-133410 v613 a

We have prepared two new silylene-phosphine-based hybrid ligands Si{N(R)C6H4(PPh2)}{PhC((NBu)-Bu-t)(2)} [R = TMS {trimethylsilyl} (1) and TBDMS {tert-butyldimethylsilyl} (2)], which possess two donor sites. Furthermore, the treatment of the bidentate ligand 1 with base metal halides {FeBr2, CoBr2, NiCl(2)middotdme [nickel chloride(II) ethylene glycol dimethyl ether]} and 2 with NiBr(2)middotdme [nickel bromide(II) ethylene glycol dimethyl ether] afforded four-coordinate six-membered metal complexes 3-6, respectively, which feature coordination from both Si(II) and P(III) sites. Subsequently, complexes 3 [(FeBr2)Si{N(SiMe3)C6H4(PPh2)}{PhC((NBu)-Bu-t)(2)}], 4 [(CoBr2)Si{N(SiMe3)C6H4(PPh2)}{PhC((NBu)-Bu-t)(2)}], 5 [(NiCl2)Si{N(SiMe3)C6H4(PPh2)}{PhC((NBu)-Bu-t)(2)}], and 6 [(NiBr2)Si{N((SiBuMe2)-Bu-t)C6H4(PPh2)}{PhC((NBu)-Bu-t)(2)}] are studied for their redox and magnetic properties with the help of UV-vis spectroscopy, cyclic voltammetry, SQUID magnetometry, and theoretical calculations. Complexes 3-6 were found to display a paramagnetic behavior. All the compounds are well established by single-crystal X-ray diffraction studies.

1 aAkhtar, Ruksana1 aKaulage, Sandeep, H.1 aSangole, Mayur, P.1 aTothadi, Srinu1 aParvathy, Parameswaran1 aParameswaran, Pattiyil1 aSingh, Kirandeep1 aKhan, Shabana uhttps://library.ncl.res.in/content/first-row-transition-metal-complexes-phosphine-silylene-based-hybrid-ligand01202nas 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-chiral01831nas a2200253 4500008004100000022001400041245014900055210006900204260000800273490000700281520097200288653001101260653001801271653001201289653001001301653001801311653001601329100002301345700002201368700002501390700001701415700001801432856012701450 2025 eng d a0947-653900aCe[N(SiMe3)2]3(THF)3-catal yzed hydroboration of CO2, esters and epoxides with pinacolborane: selective synthesis of methanol in multigram scale0 aCeNSiMe323THF3catal yzed hydroboration of CO2 esters and epoxide cMAR0 v313 a

In this work, we have reduced CO2 with HBpin to afford borylated methanol product selectively in similar to 99 % yield using Ce[N(SiMe3)(2)](3)(THF)(3) as a catalyst. This led to multigram scale isolation of methanol obtained from CO2 reduction via the hydrolysis of borylated methanol, this establishes the potential of Ce[N(SiMe3)(2)](3)(THF)(3) as an efficient homogeneous catalyst for the bulk scale methanol synthesis. A practical application of this catalytic system was also shown by reducing CO2-containing motorbike exhaust efficiently and selectively. Further, C-O bond activation of esters and epoxides using HBpin and 1-2 mol % of Ce[N(SiMe3)(2)](3)(THF)(3) at 60 degrees C afforded the borylated alcohols in good to excellent yields, which can easily be hydrolysed to the eco-friendly corresponding alcohol. The stoichiometric experiments were performed to prove the formation of in-situ generated cerium hydride [Ce]-H as an active catalyst.

10aCerium10aCO2 reduction10aEpoxide10aEster10aHydroboration10aLanthanides1 aHossain, Md, Jabed1 aShah, Brij, Kumar1 aDash, Soumya, Ranjan1 aVanka, Kumar1 aKhan, Shabana uhttps://library.ncl.res.in/content/censime323thf3-catal-yzed-hydroboration-co2-esters-and-epoxides-pinacolborane-selective01079nas a2200205 4500008004100000022001400041245008300055210006900138260000800207300001600215490000700231520039700238100002500635700002200660700002300682700002100705700001700726700001800743856011200761 2025 eng d a1359-734500aSilylene-copper(i) catalysis: regioselective protoboration of terminal alkynes0 aSilylenecopperi catalysis regioselective protoboration of termin cDEC a19652-196550 v613 a

Herein, we report an efficient regioselective protoboration of the terminal alkynes catalyzed by newly synthesized silylene-copper(i)-aryl complexes. This method offers a broad substrate scope, good functional-group compatibility, and a gram-scale synthetic ability. The insight into the mechanistic cycle is also provided with the support of experimental and theoretical studies.

1 aKaulage, Sandeep, H.1 aShah, Brij, Kumar1 aPanday, Rishukumar1 aSharma, Himanshu1 aVanka, Kumar1 aKhan, Shabana uhttps://library.ncl.res.in/content/silylene-copperi-catalysis-regioselective-protoboration-terminal-alkynes02695nas a2200241 4500008004100000022001400041245014400055210006900199260000800268300001600276490000800292520183600300100002102136700002002157700002202177700002402199700002302223700002002246700002202266700001902288700001802307856012802325 2026 eng d a0002-786300aHarnessing strong chiroptical nonlinearity in carbene-copper-amides through center-specific chirality: an approach to amplified dissymmetry0 aHarnessing strong chiroptical nonlinearity in carbenecopperamide cJUN a23238-232530 v1483 a

We present the design, synthesis, and photophysical characterization of a new class of chiral N-heterocyclic carbene (NHC)-copper(I)-amide (CMA) complexes with enantiomerically pure phenylethylamine motifs within the amide framework. These chiral CMA complexes represent a new class of mononuclear molecular Cu(I) complexes exhibiting pronounced chiral nonlinear optical (NLO) activity, which are actively being researched for advanced optoelectronic applications such as advanced photonics, biosensing, and security. The intrinsic molecular chirality and noncentrosymmetric crystal packing collectively enable strong second-harmonic generation (SHG) responses in the presence of circularly polarized (CP) light. Notably, these complexes display impressive SHG circular dichroism factors (g SHG-CD) as high as +/- 0.40 at 1000 nm, equaling or surpassing state-of-the-art chiral perovskites in this domain. Beyond their exceptional NLO response, the complexes exhibit dual emissive behavior, originating from both singlet and triplet excited states, with absolute quantum yields reaching 30%, and validated by TD-DFT calculations. The air-sensitive phosphorescence (similar to 550 nm) efficiently generates singlet oxygen (1O2), confirmed by PPh3 photooxidation and TEMPO radical generation. Remarkably, the emission can be reversibly switched between pure singlet and mixed singlet-triplet states by external modulation of O2, maintaining photostability over multiple oxic-anoxic cycles up to 5 days. These findings establish chiral CMA complexes as a new class of NHC-ligated molecular Cu(I) systems to display circularly polarized NLO activity with reversible photoluminescent switching, opening new avenues for exploring main-group organometallic compounds in next-generation polarization-sensitive photonic devices.

1 aGhosh, Moushakhi1 aTanwar, Riteeka1 aPanwaria, Prakash1 aChatterjee, Abhijit1 aPanday, Rishukumar1 aAkhtar, Ruksana1 aVenugopal, Geethu1 aMandal, Pankaj1 aKhan, Shabana uhttps://library.ncl.res.in/content/harnessing-strong-chiroptical-nonlinearity-carbene-copper-amides-through-center-specific