Sol-gel processed poly(alumosiloxanes) as carrier matrices for polymer-anchored ruthenium(II) complexes

The trimethoxysilyl-(T)-functionalized ruthenium(II) complex cis-Cl(PI)Ru(C O)(P similar to O)(3) [1(T-0)(3)] {P similar to O: P-coordinated ether-phos phine, PhP(CH2CH2OCH3)(CH2)(3)Si(OMe)(3)} is sol-gel processed with the sil icon containing co-condensation agents methyltrimethoxysilane (T-0), or dim ethyldiethoxysilane (D-0) and various amounts of aluminum-sec-butoxide [Al( OsecBu)(3)]. All components are polycondensed to result in the poly(alumosi loxane)-bound ruthenium complexes 1(T-n)(3)(T-m)(9)(Al)(z) and 1(T-n)(3)(D- i)(3)(Al)(z) (T=T-type silicon atom, three oxygen neighbors; D = D-type sil icon atom, two oxygen neighbors; i, n, m = number of Si-O-Si bonds; (Al) = (Al2O3)(1/2); z = 3, 2, 1, and 0.5). From P-31 and C-13 CP/MAS NMR as well as IR spectroscopic investigations it can be concluded that the complex fra gment cis-Cl(H)Ru(CO)(P similar to O)(3) is preserved during the immobiliza tion. Stoichiometric formulas of the polymers derived by Si-29 solid-state NMR spectroscopy and energy dispersive X-ray spectroscopy (EDX) suggest tha t the amount of aluminum can be adjusted by the applied stoichiometry. The various amounts of aluminum are reflected in the shape of the Si-29 solid s tate NMR resonances. (C) 1999 Elsevier Science B.V. All rights reserved.