142012-47-3Relevant academic research and scientific papers
Synthesis, structure, and fluxional behavior of octahedral ruthenium(II) complexes with mixed oxygen-phosphine ligands. 31P DNMR spectroscopic studies, line shape analysis, and determination of rearrangement barriers
Lindner, Ekkehard,M?ckel, Andrea,Mayer, Hermann August,Kühbauch, Hartwig,Fawzi, Riad,Steimann, Manfred
, p. 1266 - 1271 (2008/10/08)
The synthesis and spectroscopic properties of ether-phosphine ruthenium(II) complexes of the type Cl2Ru(P'down curve sign'O)2 (5a, 7a-10a) and trans-Cl2Ru(CO)(P～O)(P'down curve sign'O) (5b, 7b-10b) are reported. Temperature-dependent 31P NMR spectra of the fluxional complexes 1b-11b and cis-Cl2Ru(CO)(P～O)(P'down curve sign'O) (1c-3c) were measured and by using a modified version of DNMR5, computer-generated spectra were obtained and fitted to the experimental spectra. Graphic application of the Eyring equation to the kinetic data afforded the thermodynamic parameters ΔH≠, ΔS≠, and ΔG≠. Complex 11b with the strong basic four-membered ether-phosphine 11 crystallizes in the monoclinic space group P21/n, with a = 11.974(2) A?, b = 10.877(2) A?, c = 29.567(6) A?, β = 96.34(3)°, Z = 4, and V = 3827.2(12) A?3 (R = 0.075 and Rw = 0.076).
Ruthenium(II) Complexes with the Novel Ligand (Oxetanyl-2-methyl)diphenylphosphine
Lindner, Ekkehard,Moeckel, Andrea
, p. 693 - 696 (2007/10/02)
Key Words: Oxetanyl-Phosphine, O-Basicity, Ruthenium Complexes, Fluxional Behaviour The new ether-phosphine ligand (oxetanyl-2-methyl)diphenylphosphine (1) with strongly basic properties is obtained by reaction of LiPPh2 with 2-chloromethyloxetane.Reaction of 1 with Cl2Ru(PPh3)3 results in the formation of the bis(chelate) complex trans-Cl2Ru(PO)2 (2). (PO = η1-P-coordinated; PO = η2-O,P-coordinated).With CO only one Ru-O bond is cleaved to give the monocarbonylruthenium(II) complex trans-Cl2Ru(CO)(PO)(PO) (3). 3 shows fluxional behaviour only at higher temperatures as demonstrated by 31P NMR spectra.
