Sol-gel processed phosphine ligands with two T- or D-silyl functionalities and their (η-CMe)Ru(II) complexes
Chemistry of Materials, ISSN: 0897-4756, Vol: 11, Issue: 7, Page: 1833-1845
1999
- 9Citations
- 5Captures
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Article Description
A new class of hemilabile D- and T-functionalized ether phosphine ligands of the type MeOCHCHP[(CH)SiMe (OMe)] [3a,b,d,e(T) (m = 0: z = 3 (a), 6 (b), 8 (d), 14 (e)), and 3c(D) (m = 1; z = 6 (c))] was obtained by treatment of 2-methoxyethylphosphine (1) with the ω-alkenylsilanes HC=CH(CH)=SiMe(OMe) (2a-e). Treatment of [(η-CMe)-RuCl] with the T-silyl phosphines 3a,b,d,e(T) results in the formation of the corresponding complexes (η-CMe)RuCl{MeOCHCH P[(CH)SiMe(OMe) ]} [4a,b,d,e(T)]. In the presence of CHCN and AgSbF 4b(T) affords the cationic T-silyl complex [(η-CMe)Ru-(NCCH){MeOCH CHP[(CH)SiMe (OMe)]}]SbF [5b(T)]. 3a,b,d,e(T), 3c(D), 4a,b,d,e(T), and 5b(T) were sol-gel processed with variable amounts of the co-condensation agent (MeO)MeSi(CH)SiMe(OMe) (D-C-D) to give the stationary phases (Fn = functionality → ligands or complexes) {Fn[SiO(OX)]}{MeSiO (OX)(CH)(XO) -OSiMe}, Fn = P(CHCHOMe)[(CH)-] [3a,b,d,e(T)(D-C-D ) ≙ I, II-II, IV, V], {Fn[SiO(OX)Me]}{MeSiO (OX)(CH)(XO) OSiMe} [3c(D)(D-C-D) ≙ III], Fn = [Cp*RuCl]P(CHCHOMe)[(CH )-] [4a,b,d,e(T)(D-C-D ) ≙ VI, VII, VII, VIII, IX], and Fn = {[Cp*Ru(NCCH)]SbF} P(CHCHOMe)[(CH) -] [5b(T)-(D-C-D) ≙ X] (see Table 1) [T = T-type silicon atom (three oxygen neighbors); D = D-type silicon atom (two oxygen neighbors); n, i = number of Si-O-Si bonds; n = 0-3, i = 0-2; y = number of co-condensed D-C-D molecules]. Realistic amounts of T and D species and the degree of condensation were determined Si CP/MAS NMR spectroscopically. The polymeric phosphines I, II-II, IV, and V show higher degrees of condensation than the corresponding ruthenium(II) complexes VI, VII, VII, VIII, and IX. Bond lengths of the ruthenium(II) complex in the stationary phase VII were elucidated by an EXAFS analysis. From relaxation time studies (T, T) and cross-polarization experiments (T), it is concluded that the polymeric phosphines I, II-II, IV, and V reveal an increasing mobility with longer alkyl spacers between the polymer and the P-functionality and an increasing amount of the co-condensation agent D-C-D. Owing to the multiple fixation of the ruthenium centers to the polymeric matrixes in the stationary phases VI, VII, VII, VIII, IX, and X, the mobility in these materials is reduced. H, C-2D-WISE NMR investigations on the interphase set up by X and EtOH point to a remarkable decrease of the rigid character compared to the stationary phase X without EtOH. © 1999 American Chemical Society.
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