02047nas a2200205   4500008004100000022001400041245012200055210006900177260011000246300001200356490000600368520121100374100002501585700002301610700002301633700002001656700001801676700001901694856012801713       2015                        eng d  a2041-652000aStepwise isolation of low-valent, low-coordinate Sn and Pb mono- and dications in the coordination sphere of platinum0 aStepwise isolation of lowvalent lowcoordinate Sn and Pb mono and  aTHOMAS GRAHAM HOUSE, SCIENCE PARK, MILTON RD, CAMBRIDGE CB4 0WF, CAMBS, ENGLANDbROYAL SOC CHEMISTRYcOCT  a425-4350 v63 a<p>Synthetic access to low-coordinate Pb mono- and dications is in general impeded due to their poor solubility and highly electrophilic nature. However, the electrophilicity of these cations can be tamed by attaching them to electron-rich transition metals. Following this principle we have isolated low-valent Pb mono- ([(Cy3P)(2)Pt-PbCl](2)[AlCl4](2), 8a) and dications ([(Cy3P)(2)Pt(Pb)][AlCl4](2), 11) in the coordination sphere of platinum. The same approach then has been implemented for the isolation of analogous low-valent Sn mono- (7a) and dications (10). An energy decomposition analysis (EDA-NOCV) was performed to investigate the nature of Pt-Pb and Pb-Cl bonding in [(Cy3P)(2)Pt(PbCl2)] (2), 8a and 11. The results show that the Pt-Pb bonds in 8a and 11 are electron-sharing in nature, whereas that of the precursor 2 is a dative bond. The breakdown of attractive interactions in 2, 8a and 11 reveals that the ionic interactions in the analyzed Pt-Pb and Pb-Cl bonds are always stronger than the covalent interactions, except for the Pb-Cl bond in 8a. The calculated D3 dispersion energies show that dispersion interactions play a key role in the thermodynamic stability of 2, 8a and 11.</p>1 aBraunschweig, Holger1 aCelik, Mehmet, Ali1 aDewhurst, Rian, D.1 aHeid, Magdalena1 aHupp, Florian1 aSen, Sakya, S.  uhttps://library.ncl.res.in/content/stepwise-isolation-low-valent-low-coordinate-sn-and-pb-mono-and-dications-coordination-001721nas a2200241   4500008004100000245008700041210006900128260000800197300001600205490000800221520091800229100002501147700002001172700002501192700002301217700001901240700002301259700002201282700002301304700001901327700002001346856011301366       2016                        eng d00aDynamic, reversible oxidative addition of highly polar bonds to a transition metal0 aDynamic reversible oxidative addition of highly polar bonds to a  cDEC  a16140-161470 v1383 aThe combination of Pt complexes and indium trihalides leads to compounds that form equilibria in solution between their In X oxidative addition (OA) products (Pt indyl complexes) and their metal-only Lewis pair (MOLP) isomers (LnPt -> InX3). The position of the equilibria can be altered reversibly by changing the solvent, while the equilibria can be reversibly and irreversibly driven toward the MOLP products by addition of further donor ligands. The results mark the first observation of an equilibrium between MOLP and OA isomers, as well as the most polar bond ever observed to undergo reversible oxidative addition to a metal complex. In addition, we present the first structural characterization of MOLP and oxidative addition isomers of the same compound. The relative energies of the MOLP and OA isomers were calculated by DFT methods, and the possibility of solvent-mediated isomerization is discussed.1 aBertermann, Ruediger1 aBoehnke, Julian1 aBraunschweig, Holger1 aDewhurst, Rian, D.1 aKupfer, Thomas1 aMuessig, Jonas, H.1 aPentecost, Leanne1 aRadacki, Krzysztof1 aSen, Sakya, S.1 aVargas, Alfredo  uhttps://library.ncl.res.in/content/dynamic-reversible-oxidative-addition-highly-polar-bonds-transition-metal