01769nas a2200193 4500008004100000245006200041210005600103260000800159300001400167490000700181520119000188100002001378700001901398700001801417700001501435700001701450700001901467856008901486 2018 eng d00aAccess to silicon(II)- and germanium(II)-indium compounds0 aAccess to siliconII and germaniumIIindium compounds cAPR a1206-12130 v373 aDespite the remarkable ability of N-heterocyclic silylene to act as a Lewis base and form stable Lewis adducts with group 13 elements such as boron, aluminum, and gallium, there has been no such comparable investigation with indium and the realization of a stable silylene-indium complex has still remained elusive. Similarly, a germylene-indium complex is also presently unknown. We describe herein the reactions of [PhC(NtBu)(2)SiN-(SiMe3)(2)] (1) and [PhC(NtBu)(2)GeN(SiMe3)(2)] (4) with InCl3 and InBr3 that have resulted in the first silylene-indium complexes, [PhC(NtBu)(2)Si{N(SiMe3)(2)}-> InCl3] (2) and [PhC(NtBu)(2)Si{N(SiMe3)(2)}-> InBr3] (3), as well as the first germylene-indium complexes, [PhC(NtBu)(2)Ge{N(SiMe3)(2)}-> InCl3] (5) and [PhC(NtBu)(2)Ge{N(SiMe3)(2)}-> InBr3] (6). The solid-state structures of all species have been validated by single-crystal X-ray diffraction studies. Note that 5 and 6 are the first structurally characterized organometallic compounds that feature a Ge-In single bond (apart from the compounds in Zintl phases). Theoretical calculations reveal that the Si(II)-> In bonds in 2 and 3 and the Ge(II)-> In bonds in 5 and 6 are dative bonds.1 aPahar, Sanjukta1 aKarak, Suvendu1 aPait, Moumita1 aRaj, Vipin1 aVanka, Kumar1 aSen, Sakya, S. uhttps://library.ncl.res.in/content/access-siliconii-and-germaniumii-indium-compounds01159nas a2200205 4500008004100000022001400041245009400055210006900149260000800218300001600226490000700242520046600249100002000715700002600735700001500761700002400776700001700800700001900817856011700836 2020 eng d a1359-734500aAccess to diverse germylenes and a six-membered dialane with a flexible beta-diketiminate0 aAccess to diverse germylenes and a sixmembered dialane with a fl cOCT a11871-118740 v563 a

A nacnac-based tridentate ligand containing a picolyl group (L) was employed to isolate chlorogermylene (1). The reaction of1with another equivalent of GeCl2 center dot dioxane surprisingly gave pyridylpyrrolide-based chlorogermylene (2)viaC-N bond cleavage and C-C coupling, while with AlCl3, it afforded a transmetalated product,4. The reaction of L with AlH3 center dot NMe2Et led to an unusual cyclohexane type six-membered dialane heterocycle (5).

1 aPahar, Sanjukta1 aSwamy, V., S. V. S. N1 aDas, Tamal1 aGonnade, Rajesh, G.1 aVanka, Kumar1 aSen, Sakya, S. uhttps://library.ncl.res.in/content/access-diverse-germylenes-and-six-membered-dialane-flexible-beta-diketiminate01772nas a2200265 4500008004100000022001400041245007500055210006900130260000900199300001400208490000700222520099600229653000801225653001601233653001401249653002001263653000901283100001901292700001701311700001501328700002001343700001701363700001901380856010701399 2020 eng d a1861-472800aAmidinato germylene-zinc complexes: synthesis, bonding, and reactivity0 aAmidinato germylenezinc complexes synthesis bonding and reactivi cOCT  a3116-31210 v153 a

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)}-> 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)}-> 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.

10aDFT10aGermathione10aGermylene10aX-ray Structure10azinc1 aYadav, Sandeep1 aKumar, Rohit1 aRaj, Vipin1 aYadav, Prashant1 aVanka, Kumar1 aSen, Sakya, S. uhttps://library.ncl.res.in/content/amidinato-germylene-zinc-complexes-synthesis-bonding-and-reactivity01404nas a2200181 4500008004100000022001400041245009700055210006900152260000900221300001400230490000700244520076400251100002401015700002301039700002401062700001901086856011701105 2021 eng d a0276-733300aAccess to a variety of Ge(II) and Sn(II) compounds through substitution of hypersilyl moiety0 aAccess to a variety of GeII and SnII compounds through substitut cAUG  a2651-26570 v403 aWe have prepared amidinato-germylene (3) and -stannylene (4) with a tris(trimethylsilyl)silyl substituent and subsequently substituted the hypersilyl moiety by reacting 3 with chlorophosphines, which led to phosphino germylenes (5 and 6) with concomitant liberation of (Me3Si)(3)SiCl. Exploiting the fluoride affinity of the silicon atom, we have prepared pentafluoropyridyl germylene (7) and -stannylene (8) by reacting 3 and 4 with C5F5N with simultaneous elimination of (Me3Si)(3)SiF. These are the first examples of aryl germylenes or stannylenes prepared via C-F bond activation of a perfluoroarene. The reaction of 4 with Me3NO resulted in a novel Sn2O2 ring (9). All compounds were characterized by single-crystal X-ray structure determination studies.1 aBisai, Milan, Kumar1 aAjithkumar, V., S.1 aGonnade, Rajesh, G.1 aSen, Sakya, S. uhttps://library.ncl.res.in/content/access-variety-geii-and-snii-compounds-through-substitution-hypersilyl-moiety01939nas a2200205 4500008004100000022001400041245010700055210006900162260000800231300001400239490000700253520122500260100001801485700002101503700002501524700001901549700001701568700001901585856012901604 2023 eng d a0276-733300aActivation of the olefinic C-H bond of NHC and NHO by perimidine-based silicon and germanium compounds0 aActivation of the olefinic CH bond of NHC and NHO by perimidineb cJUL a1909-19170 v423 a

In this manuscript, several backbonegermylene-functionalized zwitterioniccompounds were prepared conveniently from the corresponding N-heterocycliccarbenes or N-heterocyclic olefins in a single step through backboneC-H activation. Our initial motivation was to generate a silylenefrom C10H6(Me3SiN)(2)SiHCl(2) using ItBu [ItBu= (1,3-ditert-butyl)imidazol-2-ylidene], but instead, the reactionled to deprotonation from the imidazolium backbone of ItBu, forming the imidazolium salt with a silyl backbone at the C4position (3). We presumed that the reaction proceededthrough the generation of an ephemeral silylene. We subsequently preparedthe analogous germylene (4) and reacted it with IDipp[IDipp = 1,3-bis(2,6-diisopropylphenyl)imidazol-2-ylidene], ItBu, and IDipp=CH2. Spectroscopic and crystallographicanalysis of these complexes revealed that, in all cases, there wasdeprotonation from the backbone and formation of zwitterionic products(5-7). When the hydrogen in the NHCbackbone was replaced with methyl groups such as IDipp(Me) (1,3-bis(2,6-diisopropylphenyl)-4,5-dimethylimidazol-2-ylidene),simple adduct formation occurred, exemplified by the isolation ofIDipp(Me)& BULL;Ge(NSiMe3)(2)C10H6 (8).

1 aGour, Kritika1 aPramanik, Debjit1 aDash, Soumya, Ranjan1 aTothadi, Srinu1 aVanka, Kumar1 aSen, Sakya, S. uhttps://library.ncl.res.in/content/activation-olefinic-c-h-bond-nhc-and-nho-perimidine-based-silicon-and-germanium-compounds02304nas a2200229 4500008004100000022001400041245011900055210006900174260000900243490000700252520151600259653001001775653002401785653002701809653001901836653001301855100001701868700002001885700001901905700001901924856013101943 2024 eng d a0947-653900aAccess to NHC-Boryl mono- and bis-selenide and utility as mild selenium transfer reagent including to the C-F bond0 aAccess to NHCBoryl mono and bisselenide and utility as mild sele cJAN 0 v303 a

Reactions of 5-SIDipp & sdot; BH3 (5-SIDipp=1,3-bis(2,6-diisopropylphenyl)-imidazolin-2-ylidene) (1) with diphenyldiselenide provide access to 5-SIDipp-boryl mono- (5-SIDipp & sdot; BH2SePh) (2) and bis-selenide (5-SIDipp & sdot; BH(SePh)2) (3). The facile cleavage of the B-Se bond makes 2 a neutral source of selenium nucleophiles in substitutions reactions with benzyl bromides, and provide access to the corresponding selenoethers. The direct transformations of one of the C(sp2)-F bonds of C5F5N and C6F5CF3 to C-Se bonds have also been achieved by the use of 2 without employing transition-metal catalysts. While it was previously established that C6F6 could undergo complete defluoroselenation under harsh conditions, we successfully achieved partial defluorination of C6F6 by employing 2 as a mild selenide transfer reagent. During the formation of C-Se bonds through the cleavage of C-F bonds, the potential by-product NHC & sdot; BH2F undergoes ring expansion of the NHC, leading to the formation of the six-membered diaazafluoroborinane (7). Access to NHC & sdot; boryl mono- and bis-selenides from NHC & sdot; BH3 has been achieved. The boryl mono selenide has been demonstrated to function as a selenium transfer reagent, enabling the synthesis of selenoethers from benzyl bromide. Additionally, it can also facilitate the conversion of the challenging aromatic C-F bond to a C-Se bond, resulting in concomitant ring expansion of NHC & sdot; haloborane.image

10aboron10aC-F Bond Activation10aN-Heterocyclic carbene10aRing expansion10aSelenium1 aKundu, Gargi1 aAmrutha, P., R.1 aTothadi, Srinu1 aSen, Sakya, S. uhttps://library.ncl.res.in/content/access-nhc-boryl-mono-and-bis-selenide-and-utility-mild-selenium-transfer-reagent-including01339nas a2200193 4500008004100000022001400041245006100055210006100116260000800177490000700185520073500192100002300927700002000950700002700970700002200997700001901019700001901038856008801057 2024 eng d a1477-922600aActivation of carbon disulfide by a hypersilyl germylene0 aActivation of carbon disulfide by a hypersilyl germylene cJUL0 v533 a

In this work, the insertion of CS2 into the Ge-Si bond of PhC(NtBu)2Ge-Si(SiMe3)3 (1) has been investigated, resulting in the formation of PhC(NtBu)2Ge-C( 00000000 00000000 00000000 00000000 11111111 00000000 11111111 00000000 00000000 00000000 S)-S-Si(SiMe3)3 (2). Interestingly, the addition of NHC to 2 allows the release of NHCCS2 with concomitant regeneration of 1. Addition of another equivalent of 1 or an analogous hypersilyl silylene, [PhC(NtBu)2Si-Si(SiMe3)3], to 2 led to the formation of compounds with a GeS (3) or a SiS (4) bond. In this work, the insertion of CS2 into the Ge-Si bond of PhC(NtBu)2Ge-Si(SiMe3)3 (1) has been investigated, resulting in the formation of PhC(NtBu)2Ge-C(S)-S-Si(SiMe3)3 (2).

1 aAjithkumar, V., S.1 aKhilari, Nripen1 aGhanwat, Pratiksha, B.1 aVenugopal, Geethu1 aKoley, Debasis1 aSen, Sakya, S. uhttps://library.ncl.res.in/content/activation-carbon-disulfide-hypersilyl-germylene