ISSN:
0009-2940
Keywords:
Ether-phosphanes
;
Ruthenium complexes
;
Polysiloxane matrices
;
CP-MAS NMR
;
Chemistry
;
Inorganic Chemistry
Source:
Wiley InterScience Backfile Collection 1832-2000
Topics:
Chemistry and Pharmacology
Notes:
Carrier-Bound Organometallic Complexes, III[1]. - Polysiloxane-Bound (Ether-phosphane)ruthenium(II) Complexes and Their CP-MAS NMR-Spectroscopic CharacterizationThe 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 mono-chelated (ether-phosphane)ruthenium(II) complex Cl2Ru(P∼O)2(P∼O) (4c) and the hydride HRuCl(CO)(P∼O)3 (5c) (P∼O: η1-P-coordinated; P∼O: η2-O∼P-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{1H}-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(P∼O)2 (6c′). In the presence of carbon monoxide there is an equilibrium between 5c′ and HRuCl(CO)2(P∼O)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 [containing ligand Ph2P(CH2)2OCH3 (1a)] and polysiloxane-bound phosphane complexes 4c′ and 5c′.
Additional Material:
3 Ill.
Type of Medium:
Electronic Resource
URL:
http://dx.doi.org/10.1002/cber.19921251110
