| Abstract: | Supported Organometallic Complexes. VI. Characterization und Reactivity of Polysiloxane-Bound (Ether-phosphane)ruthenium(II) Complexes The ligands PhP(R)CH2D R = (CH3O)3Si(CH2)3; D = CH2OCH3 ( 1b ); D = tetrahydrofuryl ( 1c ); D = 1,4-dioxanyl ( 1d )] have been used to synthesize (ether-phosphane)ruthenium(II) complexes, which have been copolymerized with Si(OEt)4 to yield polysiloxane-bound complexes. The monomers cis,cis,trans-Cl2Ru(CO)2(P ～ O)2 ( 3b ) and HRuCl(CO)(P ～ O)3 ( 5b ) were treated with NaBH4 to form cis,cis,trans-H2Ru(CO)2(P ～ O)2 ( 4b ) and H2Ru(CO)(P ～ O)3 ( 6b ), respectively (P ～ O = η1-P coordinated;  = η2-  coordinated). Addition of Si(OEt)4 and water leads to a base catalyzed hydrolysis of the silicon alkoxy-functions and a precipitation of the immobilized counterparts 4b ′, 6b ′. The polysiloxane matrix resulting by this new sol gel route has been described under quantitative aspects by 29Si CP-MAS NMR spectroscopy. 4b ′ reacts with carbon monoxide to form Ru(CO)3(P ～ O)2 ( 7b ′). Chelated polysiloxane-bound complexes Cl2Ru( )2 ( 9c ′, d ′) and Cl2Ru( )(P ～ O)2 ( 10b ′, c ′) have been synthesized by the reaction of 1b–c with Cl2Ru(PPh3)3 ( 8 ) followed by a copolymerization with Si(OEt)4. The polysiloxane-bound complexes 9c ′, d ′ and 10b ′, c ′ react with one equivalent of CO to give Cl2Ru(CO)( )(P ～ O) ( 12b ′– d ′). Excess CO leads to the all-trans-complexes Cl2Ru(CO)2(P ～ O)2 ( 14b ′– d ′), which are thermally isomerized to cis,cis,trans- 3b ′– d ′. The chemical shift anisotropy of 31P in crystalline Cl2Ru( )2 ( 9a , R = Ph, D = CH2OCH3) has been compared with polysiloxane-bound 9d ′ indicating a non-rigid behavior of the complexes in the matrix. |
