Sol-Gel Processed Phosphine Ligands with Two T- or D-Silyl Functionalities and Their (5-C5Me5)Ru(II)
详细信息 查看全文
- 作者：Ekkehard Lindner ; Wolfram Wielandt ; Andreas Baumann ; Hermann A. Mayer ; Ulrich Reinö ; hl ; Achim Weber ; Teja S. Ertel ; and Helmut Bertagnolli
- 刊名：Chemistry of Materials
- 出版年：1999
- 出版时间：July 1999
- 年：1999
- 卷：11
- 期：7
- 页码：1833 - 1845
- 全文大小：239K
- 年卷期：v.11,no.7(July 1999)
- ISSN：1520-5002
文摘
A new class of hemilabile D- and T-functionalized ether phosphine ligands of the typeMeOCH2CH2P[(CH2)zSiMem(OMe)3-m]2 [3a,b,d,e(T0) (m = 0: z = 3 (a), 6 (b), 8 (d), 14 (e)),and 3c(D0) (m = 1; z = 6 (c))] was obtained by treatment of 2-methoxyethylphosphine (1)with the 
-alkenylsilanes H2C=CH(CH2)zSiMem(OMe)3-m (2a-e). Treatment of [(
5-C5Me5)RuCl]4 with the T-silyl phosphines 3a,b,d,e(T0) results in the formation of the correspondingcomplexes (5-C5Me5)RuCl{MeOCH2CH2P[(CH2)zSiMem(OMe)3-m]2}2 [4a,b,d,e(T0)]. In thepresence of CH3CN and AgSbF6 4b(T0) affords the cationic T-silyl complex [(5-C5Me5)Ru-(NCCH3){MeOCH2CH2P[(CH2)6SiMem(OMe)3-m]2}2]+SbF6- [5b(T0)]. 3a,b,d,e(T0), 3c(D0),4a,b,d,e(T0), and 5b(T0) were sol-gel processed with variable amounts of the co-condensationagent (MeO)2MeSi(CH2)6SiMe(OMe)2 (D0-C6-D0) to give the stationary phases (Fn =functionality 
ligands or complexes) {Fn[SiOn/2(OX)3-n]2}{MeSiOi/2(OX)2-i(CH2)6(XO)2-iOi/2SiMe}y, Fn = P(CH2CH2OMe)[(CH2)z-]2 [3a,b,d,e(Tn )2(Di -C6-Di )y 
I1, II0-II4, IV1,V1], {Fn[SiOi/2(OX)2-iMe]2}{MeSiOi/2(OX)2-i(CH2)6(XO)2-iOi/2SiMe}4 [3c(Di )2(Di -C6-Di )4 III4], Fn = [Cp*RuCl]1/2P(CH2CH2OMe)[(CH2)z-]2 [4a,b,d,e(Tn )4(Di -C6-Di )y VI1, VII0,VII1, VIII1, IX1], and Fn = {[Cp*Ru(NCCH3)]+SbF6-}1/2P(CH2CH2OMe)[(CH2)6-]2 [5b(Tn )4(Di -C6-Di )4 X4] (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 D0-C6-D0 molecules]. Realistic amounts of T and D speciesand the degree of condensation were determined 29Si CP/MAS NMR spectroscopically. Thepolymeric phosphines I1, II0-II4, IV1, and V1 show higher degrees of condensation than thecorresponding ruthenium(II) complexes VI1, VII0, VII1, VIII1, and IX1. Bond lengths of theruthenium(II) complex in the stationary phase VII0 were elucidated by an EXAFS analysis.From relaxation time studies (T1P, T1
H) and cross-polarization experiments (TPH), it isconcluded that the polymeric phosphines I1, II0-II4, IV1, and V1 reveal an increasing mobilitywith longer alkyl spacers between the polymer and the P-functionality and an increasingamount of the co-condensation agent D0-C6-D0. Owing to the multiple fixation of theruthenium centers to the polymeric matrixes in the stationary phases VI1, VII0, VII1, VIII1,IX1, and X4, the mobility in these materials is reduced. 1H,13C-2D-WISE NMR investigationson the interphase set up by X4 and EtOH point to a remarkable decrease of the rigid charactercompared to the stationary phase X4 without EtOH.
-alkenylsilanes H2C=CH(CH2)zSiMem(OMe)3-m (2a-e). Treatment of [(5-C5Me5)RuCl]4 with the T-silyl phosphines 3a,b,d,e(T0) results in the formation of the correspondingcomplexes (5-C5Me5)RuCl{MeOCH2CH2P[(CH2)zSiMem(OMe)3-m]2}2 [4a,b,d,e(T0)]. In thepresence of CH3CN and AgSbF6 4b(T0) affords the cationic T-silyl complex [(5-C5Me5)Ru-(NCCH3){MeOCH2CH2P[(CH2)6SiMem(OMe)3-m]2}2]+SbF6- [5b(T0)]. 3a,b,d,e(T0), 3c(D0),4a,b,d,e(T0), and 5b(T0) were sol-gel processed with variable amounts of the co-condensationagent (MeO)2MeSi(CH2)6SiMe(OMe)2 (D0-C6-D0) to give the stationary phases (Fn =functionality ligands or complexes) {Fn[SiOn/2(OX)3-n]2}{MeSiOi/2(OX)2-i(CH2)6(XO)2-iOi/2SiMe}y, Fn = P(CH2CH2OMe)[(CH2)z-]2 [3a,b,d,e(T I1, II0-II4, IV1,V1], {Fn[SiOi/2(OX)2-iMe]2}{MeSiOi/2(OX)2-i(CH2)6(XO)2-iOi/2SiMe}4 [3c(DIII4], Fn = [Cp*RuCl]1/2P(CH2CH2OMe)[(CH2)z-]2 [4a,b,d,e(T VI1, VII0,VII1, VIII1, IX1], and Fn = {[Cp*Ru(NCCH3)]+SbF6-}1/2P(CH2CH2OMe)[(CH2)6-]2 [5b(T X4] (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 D0-C6-D0 molecules]. Realistic amounts of T and D speciesand the degree of condensation were determined 29Si CP/MAS NMR spectroscopically. Thepolymeric phosphines I1, II0-II4, IV1, and V1 show higher degrees of condensation than thecorresponding ruthenium(II) complexes VI1, VII0, VII1, VIII1, and IX1. Bond lengths of theruthenium(II) complex in the stationary phase VII0 were elucidated by an EXAFS analysis.From relaxation time studies (T1P, T1H) and cross-polarization experiments (TPH), it isconcluded that the polymeric phosphines I1, II0-II4, IV1, and V1 reveal an increasing mobilitywith longer alkyl spacers between the polymer and the P-functionality and an increasingamount of the co-condensation agent D0-C6-D0. Owing to the multiple fixation of theruthenium centers to the polymeric matrixes in the stationary phases VI1, VII0, VII1, VIII1,IX1, and X4, the mobility in these materials is reduced. 1H,13C-2D-WISE NMR investigationson the interphase set up by X4 and EtOH point to a remarkable decrease of the rigid charactercompared to the stationary phase X4 without EtOH.