58201-22-2Relevant articles and documents
Sanchez-Delgado, Roberto A.,Bradley, John S.,Wilkinson, Geoffrey
, (1976)
Structure and reactivity of the zero-valent ruthenium complex Ru(1,2-bis(diphenylphosphino)ethane)(CO)3 and the dicationic ruthenium dimer [Ru2(1,2-bis(diphenylphosphino)ethane)2(CO) 6]2+
Skoog, Steven J.,Jorgenson, Amy L.,Campbell, John P.,Douskey, Michelle L.,Munson, Eric,Gladfelter, Wayne L.
, p. 13 - 28 (2007/10/03)
The structure of Ru(dppe)(CO)3 was characterized by single crystal X-ray diffraction [monoclinic crystal system, space group P21/n, a=12.2353(2) A, b=16.0803(3) A, c=14.2451(3) A, β=111.109(1)°, V=2614.62(9) A3, Z=4] and found to be intermediate between trigonal bipyramidal and square pyramidal. One electron oxidation of Ru(dppe)(CO)3 using [(η5-C5H5)2Fe][PF6] produced [Ru2(dppe)2(CO)6][PF6]2. The dicationic complex was fully characterized by solution spectroscopic methods and by single crystal X-ray diffraction [trigonal crystal system, space group P3121, a=20.566(2) A, c=13.871(2) A, V=5080.7(8) A3, Z=3] and found to have a dimeric structure with two octahedral units sharing a common apex via a Ru(I)-Ru(I) single bond. One octahedral unit is rotated approximately 45° relative to the other, and the chelating phosphine ligand occupies sites cis and trans to the Ru(I)-Ru(I) bond. All of the carbonyl ligands were found to be terminal. The dimer was fluxional in solution and line-shape analysis of the 31P{1H} and 13C{1H} variable-temperature NMR spectra was used to investigate the exchange mechanism and evaluate the rate constants. The mechanism involved an intramolecular, two-site exchange involving pairwise bridging carbonyls and had activation parameters of 11.8±0.15 kcal mol-1 and -6.7±0.6 eu for ΔH? and ΔS? respectively. The dimer exhibited similar thermal and photochemical reactivity patterns; disproportionation occurred in CH3CN and halogen atom abstraction occurred in halogenated solvents.
