140658-03-3Relevant articles and documents
Synthesis, Crystal Structure, and Fluxional Behavior of cis-Cl2Ru(CO)(P-O)(P-O) with cis-Positioned (Ether-Phosphane) Ligands
Lindner, Ekkehard,Moeckel, Andrea,Mayer, Hermann August,Fawzi, Riad
, p. 1363 - 1368 (2007/10/02)
Reaction of ether-phosphane ligands 2a-c with Cl2Ru(PPh3)3 (1) results in the formation of the bis(chelate) complexes trans-Cl2Ru(P-O)2 (3a-c) (P-O = η1-P-coordinated; P-O = η2-O,P-coordinated).With CO both Ru-O bonds are cleaved to give all-trans-Cl2Ru(CO)2(p-O)2 (4a-c).The mono(chelate) complexes 5a-c are obtained from stoichiometric amount of 3a-c and 4a-c.Upon heating the kinetically controlled products 5a-c are transformed into the thermodynamically more stable isomers cis-Cl2Ru(CO)(P-O)(P-O) (6a-c).Both 5a-c and 6a-c show fluxional behavior.The higher coalescence temperatures and estimated ΔG(excit.) values of 6a-c (75, 67, and 70 deg C, respectively) compared to 5a-c (55, 0, and -10 deg C, respectively) indicate different exchange mechanisms for 5 and 6.According to an X-ray structure analysis, 6n crystallizes in the monoclinic space group P21/c with Z = 4.The action of CO on 6a-c affords the cis,cis-trans complexes 7a-c.Key Words: Ruthenium(II) complexes / Ether phosphanes / Fluxional behavior