143063-79-0Relevant academic research and scientific papers
Carrier-Bound Organometallic Complexes, III. Polysiloxane-Bound (Ether-phosphane)ruthenium(II) Complexes and Their CP-MAS NMR-Spectroscopic Characterization
Lindner, Ekkehard,Kemmler, Martin,Mayer, Hermann August
, p. 2385 - 2390 (2007/10/02)
The reaction of the functionalized ether-phosphane ligand CH3O(CH2)2P(Ph)(CH2)3Si(OMe)3 (1c) with Cl2Ru(PPh3)3 (2) and HRuCl(CO)(PPh3)3 (3) results in the formation of the monochelated (ether-phosphane)ruthenium(II) complex Cl2Ru(PO)2(PO) (4c) and the hydride HRuCl(CO)(PO)3 (5c) (PO: η1-P-coordinated; PO: η2-OP-coordinated).Compounds 4c and 5c are polycondensated to the corresponding polysiloxane-bound complexes 4c' and 5c'. 31P-chemical shifts of the immobilized species 4c' and 5c' in the solid-state CP-MAS NMR spectra are compared with those of the 31P-NMR spectra of monomeric complexes 4b, c and 5b, c with the ligands CH3O(CH2)2P(Ph)(CH2)3SiMe3 (1b) and 1c in solution.No change in the structure between the monomeric and polymeric species could be observed.According to 29Si CP-MAS NMR-spectroscopic investigations the polysiloxane chains are connected by ruthenium complexes to a network with favourable properties.The chelated polysiloxane-bound red complex 4c' adds CO in the solid state to give quantitatively yellow all-trans-Cl2Ru(CO)2(PO)2 (6c').In the presence of carbon monoxide there is an equilibrium between 5c' and HRuCl(CO)2(PO)2 (7c') which was also found in solution for 5b, c and 7b, c.The reactions indicate that the chemistry of polysiloxane-bound ether-phosphane complexes can well be compared with the chemistry in solution. 31P CP-MAS NMR spectra of the complexes 4c' and 5c' are strongly dominated by a chemical shift anisotropy which shows a fingerprint pattern both for monomeric crystalline complexes 4a, 5a and polysiloxane-bound phosphane complexes 4c' and 5c'.Key Words: Ether-phosphanes / Ruthenium complexes / Polysiloxane matrices / CP-MAS NMR
