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- W2068998170 abstract "Abstract The reaction of [Pd{CH 2 SiPh 2 (CH 2 NC 5 H 10 )‐κ 2 C , N }(μ‐Cl)] 2 (CH 2 NC 5 H 10 = piperidinomethyl) with KSCN led to the centrosymmetric dimer [Pd{CH 2 SiPh 2 (CH 2 NC 5 H 10 )‐κ 2 C , N }(μ‐SCN‐κ 1 S ,κ 1 N )] 2 , which features side‐on bridging thiocyanate ligands. However, the analogous reaction of the chlorido‐bridged starting material with NaN 3 yielded the dimer [Pd{CH 2 SiPh 2 (CH 2 NC 5 H 10 )‐κ 2 C , N }(μ‐N 3 ‐κ 1 κ 1 N )] 2 , in which the azido ligands exhibit end‐on coordination. This complex persists as a mixture of cis and trans isomers in solution. Lastly, the square tetrametallic complex [Pd{CH 2 SiPh 2 (CH 2 NC 5 H 10 )‐κ 2 C , N }(μ‐CN‐κ 1 C ,κ 1 N )] 4 was obtained from the reaction between the parent chlorido‐bridged complex and AgCN. In solution, this compound forms an equilibrium between the tetra‐ and trimetallic species. Thermodynamic data (equilibrium constants and free energies in CDCl 3 and C 6 D 6 , and enthalpy and entropy in CDCl 3 ) were determined and show that the formation of the trimetallic isomer is thermodynamically disfavored [ K eq = (1.93 ± 0.07) × 10 –4 mol L –1 and Δ G eq = 20.83 ± 0.11 kJ mol –1 in CDCl 3 , K eq = (4.5 ± 0.2) × 10 –5 mol L –1 and Δ G eq = 24.40 ± 0.14 kJ mol –1 in C 6 D 6 ] and that the variation in the enthalpy and entropy are positive (Δ H = 75 ± 5 kJ mol –1 and Δ S = 186 ± 15 J mol –1 K –1 in CDCl 3 )." @default.
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- W2068998170 date "2012-06-01" @default.
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- W2068998170 title "Bridging Pseudohalides in Palladacycles as a Source of Different Assemblies" @default.
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- W2068998170 doi "https://doi.org/10.1002/ejic.201200247" @default.
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