80446-33-9Relevant academic research and scientific papers
Ruthenium(II) complexes of benzylphosphines
Wilkes, Linda M.,Nelson, John H.,Mitchener, Joseph P.,Babich, Michael W.,Riley, Walter C.,Helland, Barbara J.,Jacobson, Robert A.,Cheng, Meng Yu,Seff, Karl,McCusker, Lynne B.
, p. 1376 - 1382 (2008/10/08)
Reaction of the benzylphenylphosphines BzlnPPh3-n (L) with Ru(CO)2Cl2 produces the kinetically stable trans-L2Ru(CO)2Cl2 (1), which thermally isomerize to the thermodynamically stable cis-L2Ru(CO)2Cl2 (2). The kinetics, activation thermodynamics, and mechanisms of these processes were determined by 31P NMR spectroscopy. The isomerization is a dissociative process (ΔS≠ and ΔH≠ are both positive) whose rate increases with an increase in the steric bulk of the phosphine and is retarded by excess carbon monoxide. A series of six complexes have been characterized by elemental analyses and infrared and 1H, 13C{1H}, and 31P NMR spectroscopies. The crystal structures of trans-(Bzl3P)2Ru(CO)2Cl2 and cis-(BzlPPh2)2Ru(CO)2Cl2 have been determined from three-dimensional X-ray diffraction techniques. The structural data form a basis for discussion of the relative thermodynamic and kinetic stabilities of the isomers formed.
