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    A Zwitterionic Tetrastanna(II) Cyclic Crown
    (John Wiley and Sons Inc, 2023) Sahoo, Padmini; Chibde, Purva; Das, Satyabrata; Banerjee, Subhrashis; Vanka, Kumar; Gonnade, Rajesh G.; Yıldız, Cem. B.; Majumdar, Moumita
    A 12-membered zwitterionic tetrastanna(II) cycle 1 having a crown ether-like topology has been isolated from the deprotonation of 1,1?-methylenediimidazole (B) with two equivalents of Sn[N(SiMe3)2]2 (A). The solid-state structure and NMR analysis confirms the tetrastanna(II) cycle 1 to be comprised of two stannate(II) and two stannyliumylidene ion pairs in alternating positions of the heterocycle. Computational analysis shows greater nucleophilicity at the proximally located stannate(II) centers. Nonetheless, the tetrastanna(II) cycle 1 remains poorly reactive due to engagement of SnII lone pair electrons in intramolecular donor-acceptor interactions. Simple deprotonation reaction between Sn[N(SiMe3)2]2 (A) and N-(diisopropylphenyl)imidazole (C) in equimolar ratio has led to a stannylene 2, involving the formation of a Sn?C covalent bond with the anionic imidazol-2-yl carbon center along with the release of NH(SiMe3)2. Compound 2 exists as a dimer, where the unsubstituted ring nitrogen atom coordinated intermolecularly to the other stannylene center.
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    Intramolecular donor-stabilized tetra-coordinated germanium(iv) di-cations and their Lewis acidic properties
    (Royal Society of Chemistry, 2023) Yıldız, Cem Burak; Khan, Souvik; Gonnade, Rajesh G.; Majumdar, Moumita
    We report the first examples of intramolecular phosphine-stabilized tetra-coordinated germanium(iv) di-cationic compounds: [LiPr2Ge][CF3SO3]23iPr and [LPh2Ge][CF3SO3]23Ph (LiPr = 6-(diisopropylphosphanyl)-1,2-dihydroacenaphthylene-5-ide; LPh = 6-(diphenylphosphanyl)-1,2-dihydroacenaphthylene-5-ide). The step wise synthetic strategy involves the isolation of neutral and mono-cationic Ge(iv) precursors: [LiPr2GeCl][X] (X = GeCl31iPr, OTf 2iPr), [LPh2GeCl2] 1Ph and [LPh2GeCl][OTf] 2Ph. Both 3iPr and 3Ph exhibit constrained spiro-geometry. DFT studies reveal the dispersion of di-cationic charges over P-Ge-P sites. Anion or Lewis base binding occurs at the Ge site resulting in relaxed distorted trigonal bipyramidal/tetrahedral geometry. 3iPr and 3Ph activate the Si-H bond initially at the P-site. The hydride ultimately migrates to the Ge-site rapidly giving [LPh2GeH][CF3SO3] 3PhH, while sluggishly forming [LiPr2GeH][CF3SO3] 3iPrH. Compounds 3iPr and 3Ph were tested as catalysts for the hydrosilylation of aromatic aldehydes. While catalytic hydrosilylation proceeded via the initial Et3Si-H bond activation in the case of 3iPr, compound 3Ph as a catalyst showed a masked Frustrated Lewis Pair (FLP) type reactivity in the catalytic cycle.
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    Stabilization of the elusive antimony(I) cation and Its coordination complexes with transition metals
    (John Wiley and Sons Inc, 2021) Kumar, Vikas; Gonnade, Rajesh G.; Yıldız, Cem Burak; Majumbar, Moumita
    Upon stabilization by 5,6-bis(diisopropylphosphino)acenaphthene to form compound 1, the fugitive antimony (I) cation exhibited nucleophilic behavior towards coinage metals. Compound 1 was strategically synthesized at room temperature from SbCl3, the bis(phosphine), and trimethylsilyl trifluoromethanesulfonate taken in a 1:2:3 ratio, whereby the bis(phosphine) plays the dual role of a reductant and a supporting ligand. The generation of 1 involves two-electron oxidation of the ligand to form a P?P bonded diphosphonium dication. Compound 1 was separated from this dication to give both products in pure form in moderate yields. Despite the overall positive charge, the SbI site in 1 was found to bind to metal centers, forming complexes with AuI, AgI and CuI. Compound 1 reduced CuII to CuI and formed a coordination complex with the resulting CuI species. The effects of the electron-rich bis(phosphine) and the constrained peri geometry in stabilizing and enhancing the nucleophilicity of 1 have been rationalized through computational studies.