01877nas a2200241   4500008004100000022001400041245010600055210006900161260000800230300001600238490000700254520106200261653002301323653002301346653002001369653002201389653001401411100001701425700002401442700002001466700002201486856012701508       2021                        eng d  a1433-785100aStabilization of the elusive antimony(I) cation and its coordination complexes with transition metals0 aStabilization of the elusive antimonyI cation and its coordinati  cNOV  a25522-255290 v603 aUpon 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 Sb-I site in 1 was found to bind to metal centers, forming complexes with Au-I, Ag-I and Cu-I. Compound 1 reduced Cu-II to Cu-I and formed a coordination complex with the resulting Cu-I 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.10aantimony(I) cation10acoordination modes10anucleophilicity10aphosphine ligands10areduction1 aKumar, Vikas1 aGonnade, Rajesh, G.1 aYildiz, Cem, B.1 aMajumdar, Moumita  uhttps://library.ncl.res.in/content/stabilization-elusive-antimonyi-cation-and-its-coordination-complexes-transition-metals02021nas a2200193   4500008004100000022001400041245012200055210006900177260000900246300001600255490000700271520131500278100002301593700001701616700002401633700002001657700002201677856012801699       2023                        eng d  a2041-652000aIntramolecular donor-stabilized tetra-coordinated germanium(<sc>iv</sc>) di-cations and their Lewis acidic properties0 aIntramolecular donorstabilized tetracoordinated germaniumscivsc   cDEC   a13755-137640 v143 a<p>
	We report the first examples of intramolecular phosphine-stabilized tetra-coordinated germanium(iv) di-cationic compounds: [(L2Ge)-Ge-iPr][CF3SO3](2)3iPr and [(L2Ge)-Ge-Ph][CF3SO3](2)3Ph (L-iPr = 6-(diisopropylphosphanyl)-1,2-dihydroacenaphthylene-5-ide; L-Ph = 6-(diphenylphosphanyl)-1,2-dihydroacenaphthylene-5-ide). The step wise synthetic strategy involves the isolation of neutral and mono-cationic Ge(iv) precursors: [(L2GeCl)-Ge-iPr][X] (X = GeCl(3)1iPr, OTf 2iPr), [(L2GeCl2)-Ge-Ph] 1Ph and [(L2GeCl)-Ge-Ph][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 [(L2GeH)-Ge-Ph][CF3SO3] 3PhH, while sluggishly forming [(L2GeH)-Ge-iPr][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.</p>
1 aPeddi, Balakrishna1 aKhan, Souvik1 aGonnade, Rajesh, G.1 aYildiz, Cem, B.1 aMajumdar, Moumita  uhttps://library.ncl.res.in/content/intramolecular-donor-stabilized-tetra-coordinated-germaniumiv-di-cations-and-their-lewis02220nas a2200289   4500008004100000245011500041210006900156260000800225300000900233490000700242520124100249100002501490700002301515700002601538700001701564700002301581700002101604700002901625700002801654700001701682700002101699700002101720700002401741700002001765700002201785856012301807       2026                        eng d00aSmallest acyclic tricationic molecule containing a Bis(phosphine)-stabilized low-valent triantimony-based Unit0 aSmallest acyclic tricationic molecule containing a Bisphosphines  cMAR  a26970 v173 a<p>
	Element-element bonded multiply charged cationic species are well known as dimers or small cyclic oligomers in the condensed phase. However, the smallest acyclic version, a trinuclear unit possessing greater than a monocationic charge, has remained elusive. Here we introduce a bis(phosphine) supported low valent triantimony-based tricationic compound as a new entrant in this field. Structural elucidation and electronic understanding reveal a W-shaped tricationic unit comprising of a three-center four-electron sigma-bonded triantimony moiety that is terminally capped by bis(phosphine) ligands, with the central antimony atom having two lone pairs of electrons. The unique counter trianion [Sb(O)2(OTf)4]3- (OTf = CF3SO3) possesses reactive polar Sb delta+-O delta- bonds, the structure of which is determined from single crystal X-ray diffraction analysis. The ensemble of reactive molecular fragments found in this highly charged antimony-based compound makes it thermally unstable. Nonetheless, this fully characterized fleeting species shows a diverse reactivity profile, advancing the isolation of various novel antimony compounds, including the formation of a distinct low-valent antimony-cobalt carbonyl cluster.</p>
1 aMukherjee, Nilanjana1 aPeerless, Benjamin1 aNadurata, Vincent, L.1 aKumar, Vikas1 aSangole, Mayur, P.1 aSingh, Kirandeep1 aWiedemann, Haakon, T. A.1 aKay, Christopher, W. M.1 aKruk, Robert1 aWeigend, Florian1 aDehnen, Stefanie1 aGonnade, Rajesh, G.1 aYildiz, Cem, B.1 aMajumdar, Moumita  uhttps://library.ncl.res.in/content/smallest-acyclic-tricationic-molecule-containing-bisphosphine-stabilized-low-valent