02059nas a2200265   4500008004100000022001400041245010900055210006900164260000900233300001400242490000700256520119300263653001701456653001601473653001801489653002501507653001501532100001801547700002301565700001701588700001501605700002001620700002201640856013101662       2021                        eng d  a1861-472800aIntramolecularly double-donor-stabilized stannylene and its coordination towards Ag(I) and Au(I) centers0 aIntramolecularly doubledonorstabilized stannylene and its coordi  cAUG   a2118-21250 v163 aThe intramolecularly double-donor-stabilized stannylene 1 has been synthesized from the salt-metathesis reaction between two equivalents of lithium pyridine ene-amide L1 and SnCl2. Compound 1 exhibits dipolar behavior when reacted with B(C6F5)(3) leading to the zwitterionic compound 2. The reaction of 1 with one equivalent and 0.5 equivalent of AgOTf (OTf=trifluoromethane sulfonate) result in the formation of a stannylene-AgOTf complex 3 and a homoleptic distannylene-silver ionic complex 4, respectively. Analogous to complex 4, the gold(I) complex 5 has been synthesized from the reaction between two equivalents of 1 and 0.5 equivalent of AuCl.SMe2/Me3SiOTf. Complex 5 is the first example of homoleptic stannylene-Au(I) ionic complex among the very scarce reports on stannylene-gold(I) coordination complexes. All compounds have been structurally characterized using single crystal X-ray crystallography. Solution-state characterization have been performed using multinuclear NMR techniques. Detailed DFT calculations on the optimized geometries 1 o, 3 o-5 o reveal the change in sp- hybridization on the pyramidal Sn(II) center upon metal coordination and their bonding overlaps.10acoordination10agold cation10ahybridization10aintramolecular donor10astannylene1 aChibde, Purva1 aRaut, Ravindra, K.1 aKumar, Vikas1 aDeb, Rahul1 aGonnade, Rajesh1 aMajumdar, Moumita  uhttp://library.ncl.res.in/content/intramolecularly-double-donor-stabilized-stannylene-and-its-coordination-towards-agi-and-aui02020nas 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