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Mears, Kristian; Nguyen, Gia-Ann; Ruiz, Bronson; Zou, Wenxing; Fettinger, James C; Power, Philip P (, Chemical Communications)Half a century since the photocatalytic disproportionation of Lappert's dialkyl stannylene SnR 2 , R = CH(SiMe 3 ) 2 (1) gave the persistent trivalent radical [·SnR 3 ], the characterization of the corresponding Sn(I) product, ·SnR is now described. It was isolated as the hexastannaprismane Sn 6 R 6 (2), from the reduction of 1 by the Mg(I)-reagent, Mg(BDI Dip ) 2 , (BDI = (DipNCMe) 2 CH, Dip + 2,6-diisopropylphenyl).more » « less
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Zou, Wenxing; Fettinger, James C.; Vasko, Petra; Power, Philip P. (, Organometallics)
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Zou, Wenxing; Bursch, Markus; Mears, Kristian L.; Stennett, Cary R.; Yu, Ping; Fettinger, James C.; Grimme, Stefan; Power, Philip P. (, Angewandte Chemie International Edition)Abstract Reaction of {LiC6H2−2,4,6‐Cyp3⋅Et2O}2(Cyp=cyclopentyl) (1) of the new dispersion energy donor (DED) ligand, 2,4,6‐triscyclopentylphenyl with SnCl2afforded a mixture of the distannene {Sn(C6H2−2,4,6‐Cyp3)2}2(2), and the cyclotristannane {Sn(C6H2−2,4,6‐Cyp3)2}3(3).2is favored in solution at higher temperature (345 K or above) whereas3is preferred near 298 K. Van't Hoff analysis revealed the3to2conversion has a ΔH=33.36 kcal mol−1and ΔS=0.102 kcal mol−1 K−1, which gives a ΔG300 K=+2.86 kcal mol−1, showing that the conversion of3to2is an endergonic process. Computational studies show that DED stabilization in3is −28.5 kcal mol−1per {Sn(C6H2−2,4,6‐Cyp3)2unit, which exceeds the DED energy in2of −16.3 kcal mol−1per unit. The data clearly show that dispersion interactions are the main arbiter of the3to2equilibrium. Both2and3possess large dispersion stabilization energies which suppress monomer dissociation (supported by EDA results).more » « less
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