127253-35-4Relevant academic research and scientific papers
Ground-state versus transition-state effects in arene displacement reactions of the complexes (η6-arene)Cr(CO)s: Linear dependence of transition-state energies and resonance energies of the arene ligands
Zhang, Songshen,Shen, Jian Kun,Basolo, Fred,Ju, Telvin D.,Lang, Russell F.,Kiss, Gabor,Hoff, Carl D.
, p. 3692 - 3702 (2008/10/08)
The rates of displacement of arene and thiophene ligands by P(n-Bu)3 in decalin and PPh3 in toluene have been studied. The reactions are first order in complex and incoming ligand. Rates of reaction increase in the order benzene dimethylthiophene > triphenylene > phenanthrene > thiophene > naphthalene > anthracene > pyrene and spans about 7 kcal/mol. The combination of kinetic and thermodynamic data is used to construct reaction profiles for these reactions. On the basis of the assumption that the transition state occurs on the way to formation of (η4-arene)Cr(CO)3(L) a linear correlation exists between the enthalpy of formation of the transition-state complex and changes in resonance energy of the fused arene ligands attributable to localization of the π bonds of the proposed η4 intermediate. The rate of binding of C6H6 to (THF)3Cr(CO)3 is 10% slower than for C6D6, implicating the importance of (η1-C6H6)Cr(CO)3(THF) 2 as an intermediate on the pathway to formation of (η6-C6H6)-Cr(CO)3.
Electrochemical Syntheses, VI. Electrochemical Substitution of VIB-Hexacarbonyls M(CO)6 (M=Cr, Mo, W)
Grobe, Joseph,Zimmermann, Heinz
, p. 301 - 306 (2007/10/02)
The electrochemical substitution of group VIB hexacarbonyls by solvent molecules and/or phosphane ligands is studied in some detail and is found to be a fruitful alternative preparative route to the well-known photochemical reaction. - Keywords: Electrochemical Synthesis, Metal Carbonyls, Substitution Products, Phosphane Ligands
