01876nas a2200241   4500008004100000022001400041245010600055210006900161260000800230300001600238490000700254520106200261653002301323653002301346653002001369653002201389653001401411100001701425700002401442700002001466700002201486856012601508       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  uhttp://library.ncl.res.in/content/stabilization-elusive-antimonyi-cation-and-its-coordination-complexes-transition-metals02020nas a2200193   4500008004100000022001400041245012200055210006900177260000900246300001600255490000700271520131500278100002301593700001701616700002401633700002001657700002201677856012701699       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  uhttp://library.ncl.res.in/content/intramolecular-donor-stabilized-tetra-coordinated-germaniumiv-di-cations-and-their-lewis