Functional Polyethylene Glycol with Carboxyl-supported Platinum as an Efficient Catalysis System for the Hydrosilylation of Alkenes

Abstract

Abstract: A series of carboxylated long chain polyethylene glycols (abbreviated as PEGCOOH) has been synthesized and used to support chloroplatinic acid.These supported catalysts were then tested for their efficiency in the hydrosilylation of alkenes.The factors affecting their catalytic properties,e.g.relative molecular mass of polyethylene glycol,reaction temperature,platinum content,and type of alkenes,have been studied.It was found that the activity of the platinum catalyst decreased with increasing length of the polyethylene glycol chain,and increased with reaction temperature.Moreover,these catalysts could be reused several times without a noticeable decrease in activity or selectivity.The reaction pathway leading to excellent selectivity for the β-adduct of hydrosilylation of alkenes with triethoxysilane catalyzed by this catalysis system was discussed.

Key words: polyethylene glycol, modification, platinum, hydrosilylation, alkene

摘要： A series of carboxylated long chain polyethylene glycols (abbreviated as PEGCOOH) has been synthesized and used to support chloroplatinic acid.These supported catalysts were then tested for their efficiency in the hydrosilylation of alkenes.The factors affecting their catalytic properties,e.g.relative molecular mass of polyethylene glycol,reaction temperature,platinum content,and type of alkenes,have been studied.It was found that the activity of the platinum catalyst decreased with increasing length of the polyethylene glycol chain,and increased with reaction temperature.Moreover,these catalysts could be reused several times without a noticeable decrease in activity or selectivity.The reaction pathway leading to excellent selectivity for the β-adduct of hydrosilylation of alkenes with triethoxysilane catalyzed by this catalysis system was discussed.

关键词: polyethylene glycol, modification, platinum, hydrosilylation, alkene

BAI Ying, PENG Jiajian, YANG Hu, LI Jiayun, LAI Guoqiao, LI Xiaonian. Functional Polyethylene Glycol with Carboxyl-supported Platinum as an Efficient Catalysis System for the Hydrosilylation of Alkenes[J]. Chin.J.Chem.Eng., 2012, 20(2): 246-253.

白赢, 彭家建, 杨虎, 厉嘉云, 来国桥, 李小年. Functional Polyethylene Glycol with Carboxyl-supported Platinum as an Efficient Catalysis System for the Hydrosilylation of Alkenes[J]. Chinese Journal of Chemical Engineering, 2012, 20(2): 246-253.

References

1 Marciniec,B.,“Catalysis by transition metal complexes of alkene silylation—Recent progress and mechanistic implications”,Coord. Chem.Rev.,249(21-22),2374-2390(2005).
2 Marciniec,B.,Comprehensive Handbook on Hydrosilylation,Pergamon Press,Oxford,England(1992).
3 Roy,A.K.,“A review of recent progress in catalyzed homogeneous hydrosilation(hydrosilylation)”,Adv.Organomet.Chem.,55,1-59 (2007).
4 Speier,J.L.,Webster,J.A.,Barnes,G.H.,“The addition of silicon hydrides to olefinic double bonds.Part II.The use of group VIII metal catalysts”,J.Am.Chem.Soc.,79(4),974-979(1957).
5 Saam,J.C.,Speier,J.L.,“The addition of silicon hydrides to olefinic double bonds.Part III.The addition to non-terminal olefins in the presence of chloroplatinic acid”,J.Am.Chem.Soc.,80(15),4104-4106(1958).
6 Speier,J.L.,“Homogeneous catalysis of hydrosilylation by transition metals”,Adv.Organomet.Chem.,17,407-447(1979).
7 Karstedt,B.D.,Scotia,N.Y.,“Platinum complexes of unsaturated siloxanes and platinum containing organopolysiloxanes”,U.S.Pat.,3775452(1973).
8 Chandra,G.,Lo,P.Y.,Hitchcock,P.B.,Lappert,M.F.,“A convenient and novel route to bis(.eta.-alkyne)platinum(0)and other platinum(0) complexes from Speier’s hydrosilylation catalyst H₂[PtCl₆]·xH₂O. X-ray structure of[Pt{(.eta-CH₂ CHSiMe₂)₂O}(P-t-Bu₃)]”, Organometallics,6(1),191-192(1987).
9 Lewis,L.N.,Colborn,R.E.,Grade,H.,Bryant,G.L.,Sumpter,C.A., Scott,R.A.,“Mechanism of formation of platinum(0)complexes containing silicon-vinyl ligands”,Organometallics,14(5),2202-2213 (1995).
10 Sprengers,J.W.,Mars,M.J.,Duin,M.A.,Cavell,K.J.,Elsevier,C.J., “Selective hydrosilylation of styrene using an in situ formed platinum(1,3-dimesityl-dihydroimidazol-2-ylidene)catalyst”,J.Organomet. Chem.,679(2),149-152(2003).
11 Buisine,O.,Berthon-Gelloz,G.,Brière,J.F.,Stérin,S.,Mignani,G.,Branlard,P.,Tinant,B.,Declercq,J.P.,Marko,I.E.,“Second generation N-heterocyclic carbene-Pt(0)complexes as efficient catalysts for the hydrosilylation of alkenes”,Chem.Commun.,(30),3856-3858 (2005).
12 Prignano,A.L.,Trogler,W.C.,“Silica-supported bis(trialkylphosphine) platinum oxalates.Photogenerated catalysts for hydrosilylation of olefins”,J.Am.Chem.Soc.,109(12),3586-3595(1987).
13 Liedtke,J.,Loss,S.,Alcaraz,G.,Gramlich,V.,Grutzmacher,H., “Very stable phosphiranes”,Angew.Chem.Int.Ed.,38(11),1623-1626(1999).
14 Liedtke,J.,Loss,S.,Widauer,C.,Grutzmacher,H.,“Phosphiranes as ligands for platinum catalyzed hydrosilylations”,Tetrahedron,56(1),143-156(2000).
15 Murphy,P.J.,Spencer,J.L.,Procter,G.,“Allylsilanes in organic synthesis;convenient preparation of synthetic intermediates by catalytic hydrosilation of acetylenic alcohols”,Tetrahedron Lett.,31(7),1051-1054(1990).
16 Hu,C.Y.,Han,X.M.,Jiang,Y.Y.,“Hydrosilylation of acetylene catalyzed by a sulfur-containing polysiloxane platinum complex”,J. Mol.Catal.,35(3),329-333(1986).
17 Chen,Y.M.,Lu,X.R.,Zhong,Z.L.,“Synthesis of poly-4,7dithianonylsesquisiloxane platinum complex and its catalytic activity on hydrosilylation of olefins with triethoxysilane”,Appl.Chem.,9 (3),26-30(1992).(in Chinese)
18 Madine,J.W.,Wang,X.,Widenhoefer,R.,“Cyclization/hydrosilylation of functionalized diynes catalyzed by a cationic platinum phenanthroline complex”,Org.Lett.,3(3),385-388(2001).
19 Wang,X.,Chakrapani,H.,Madine,J.W.,Keyerleber,M.A.,Widenhoefer,R.A.,“Cyclization/hydrosilylation of functionalized 1,6-diynes catalyzed by cationic platinum complexes containing bidentate nitrogen ligands”,J.Org.Chem.,67(9),2778-2788(2002).
20 Drake,R.,Dunn,R.,Sherrington,D.C.,Thomson,S.J.,“Remarkable activity,selectivity and stability of polymer-supported Pt catalysts in room temperature,solvent-less,alkene hydrosilylations”,Chem. Commun.,(19),1931-1932(2000).
21 Drake,R.,Dunn,R.,Sherrington,D.C.,Thomson,S.J.,“Polymethacrylate and polystyrene-based resin-supported Pt catalysts in room temperature,solvent-less,l-octene hydrosilylations using trichlorosilane and methyldichlorosilane”,J.Mol.Catal.A:Chem.,177(1),49-69(2001).
22 Hu,R.H.,Zha,L.F.,Cai,M.Z.,“MCM-41-supported mercapto platinum complex as a highly efficient catalyst for the hydrosilylation of olefins with triethoxysilane”,Catal.Commun.,11(6),563-566(2010).
23 Geldbach,T.J.,Zhao,D.B.,Castillo,N.C.,Laurenczy,G.,Weyershausen,B.,Dyson,P.J.,“Biphasic hydrosilylation in ionic liquids:A process set for industrial implementation”,J.Am.Chem.Soc.,128 (30),9773-9780(2006).
24 Peng,J.J.,Li,J.Y.,Bai,Y.,Gao,W.H.,Qiu,H.Y.,Wu,H.,Deng,Y.,Lai,G.Q.,“Rh(PPh₃)3Cl/ionic liquid(molten salt)as a thermoregulated and recyclable catalytic system for hydrosilylation”,J.Mol. Catal.A:Chem.,278(1-2),97-101(2007).
25 Peng,J.J.,Li,J.Y.,Bai,Y.,Qiu,H.Y.,Jiang,K.Z.,Jiang,J.X.,Lai, G.Q.,“Ionic liquid(molten salt):Thermoregulated catalyst support for catalytic hydrosilylation process”,Catal.Commun.,9(13),2236-2238(2008).
26 Hofmann,N.,Bauer,A.,Frey,T.,Auer,M.,Stanjek,V.,Schulz,P.S., Taccardi,N.,Wasserscheid,P.,“Liquid-liquid biphasic,platinum-catalyzed hydrosilylation of allyl chloride with trichlorosilane using an ionic liquid catalyst phase in a continuous loop reactor”, Adv.Synth.Catal.,350(16),2599-2609(2008).
27 Fan,Q.H.,Deng,G.J.,Lin,C.C.,Chan,A.S.C.,“Preparation and use of MeO-PEG-supported chiral diphosphine ligands:Soluble polymer-supported catalysts for asymmetric hydrogenation”,Tetrahedron: Asymmetry,12(8),1241-1248(2001).
28 Guerreiro,P.,Ratovelomanana-Vidal,V.,Genêt,J.P.,Dellis,P., “Recyclable diguanidinium-BINAP and PEG-BINAP supported catalysts:Syntheses and use in Rh(I)and Ru(II)asymmetric hydrogenation reactions”,Tetrahedron Lett.,42(20),3423-3426(2001).
29 Chen,W.,Hems,W.,King,F.,Xiao,J.,“Asymmetric hydrogenation of ketones with polymer-supported chiral 1,2-diphenylethylenediamine”, Org.Lett.,5(24),4559-4561(2003).
30 Bergbreiter,D.E.,Osburn,P.L.,Liu,Y.S.,“Tridentate SCS palladium(II)complexes:New,highly stable,recyclable catalysts for the Reck reaction”,J.Am.Chem.Soc.,121(41),9531-9538(1999).
31 Panda,A.G.,Tambade,P.J.,Patil,Y.P.,Bhanage,B.M.,“Hydroformylation of allyl acetate using rhodium polyether diphosphinite catalyst”,React.Kinet.Mech.Cat.,99(1),143-148(2010).
32 Glos,M.,Reiser,O.,“Aza-bis(oxazolines):New chiral ligands for asymmetriccatalysis”,Org.Lett.,2(14),2045-2048(2000).
33 Yao,Q.,“A soluble polymer-bound ruthenium carbene complex:A robust and reusable catalyst for ring-closing olefin metathesis”, Angew.Chem.Int.Ed.,39(21),3896-3898(2000).
34 Varray,S.,Lazaro,R.,Martinez,J.,Lamaty F.,“New soluble-polymer bound ruthenium carbene catalysts:Synthesis,characterization,and application to ring-closing metathesis”,Organometallics,22(12),2426-2435(2003).
35 Reger,T.S.,Janda,K.D.,“Polymer-supported(salen)Mn catalysts for asymmetric epoxidation:A comparison between soluble and insoluble matrices”,J.Am.Chem.Soc.,122(29),6929-6934(2000).
36 Zhang,J.L.,Che,C.M.,“Soluble polymer-supported ruthenium porphyrin catalysts for epoxidation,cyclopropanation,and aziridination of alkenes”,Org.Lett.,4(11),1911-1914(2002).
37 Guo,H.,Shi,X.,Qiao,Z.,Hou,S.,Wang,M.,“Efficient soluble polymer-supported sharpless alkene epoxidation catalysts”,Chem. Commun.,3(2),118-119(2002).
38 Cohen,M.,Neumann,R.,“Silica tethered with poly(ethylene and/propylene)oxide as supports for polyoxometalates in catalytic oxidation”,J.Mol.Catal.A:Chem.,146(1-2),291-298(1999).
39 Chen,R.F.,Liu,X.Z.,Jin,Z.L.,“Thermoregulated phase-transfer ligands and catalysis.Part VI.Two-phase hydroformylation of styrene catalyzed by the thermoregulated phase-transfer catalyst OPGPP/Rh”,J.Organomet.Chem.,571(2),201-204(1998).
40 Jiang,J.Y.,Wang,Y.H.,Liu,C.,Xiao,Q.M.,Jin,Z.L.,“Thermoregulated phase transfer ligands and catalysis XIV:Synthesis of N,N-dipolyoxyethylene-substituted-4-(diphenylphosphino)benzenesulfonamide(PEO-DPPSA)and the catalytic activity of its rhodium complex in hydroformylation of 1-decene”,J.Mol.Catal.A: Chem.,171(1-2),85-89(2001).
41 Liu,C.,Jiang,J.Y.,Wang,Y.H.,Cheng,F.,Jin,Z.L.,“Thermoregulated phase transfer ligands and catalysis XVIII:Synthesis of N,N-dipolyoxyethylene-substituted-2-(diphenylphosphino)phenylam ine(PEO-DPPPA)and the catalytic activity of its rhodium complex in the aqueous-organic biphasic hydroformylation of 1-decene”,J. Mol.Catal.A:Chem.,198(1-2),23-27(2003).
42 Chen,R.F.,Jiang,J.Y.,Wang,Y.H.,Jin,Z.L.,“Thermoregulated phase-transfer ligands and catalysis:VIII.Two-phase hydroformylation of 4-isobutylstyrene catalyzed by thermoregulated phase-transfer catalyst OPGPP/Rh”,J.Mol.Catal.A:Chem.,149(1-2),113-117(1999).
43 Zheng,X.L.,Jiang,J.Y.,Liu,X.Z.,Jin,Z.L.,“Thermoregulated phase transfer ligands and catalysis.III.Aqueous/organic two-phase hydroformylation of higher olefins by thermoregulated phase-transfer catalysis”,Catal.Today,44(1-4),175-182(1998).
44 Wang,Y.H.,Jiang,J.Y.,Miao,Q.,Wu,X.W.,Jin,Z.L.,“Thermoregulated phase transfer ligands and catalysis:Part XIII.Use of nonionic water-soluble phosphine ligands to effect homogeneous catalyst separation and recycling”,Catal.Today,74(1-2),85-90 (2002).
45 Bai,Y.,Peng,J.J.,Li,J.Y.,Lai,G.Q.,“Use of carboxylated polyethylene glycol as promoter for platinum-catalyzed hydrosilylation of alkenes”,Appl.Organomet.Chem.,25(5),400-405(2011).
46 Luo,Y.,Dai,Y.F.,Zhu,W.B.,Fu,M.,“Silica gel supported platinum and PEG complex catalyst for hydrosilylation of styrene”,New Chem.Mater.,35(10),17-29(2007).(in Chinese)
47 Li,J.,Yang,C.H.,Zhang,L.,Ma,T.L.,“A novel fumed silica-supported nitrogenous platinum complex as a highly efficient catalyst for the hydrosilylation of olefins with triethoxysilane”,J. Organomet.Chem.,696(9),1845-1849(2011).
48 Sakaki,S.,Mizoe,N.,Sugimoto,M.,“Theoretical study of platinum(0)-catalyzed hydrosilylation of ethylene.Chalk-Harrod mechanism or modified Chalk-Harrod mechanism”,Organometallics,17 (12),2510-2525(1998).
49 Sakaki,S.,Ogawa,M.,Musashi,Y.,“C₂H₄ insertion into Pt(II)SiH3 and Pt(II)H bonds.An ab initio MO/MP4 study”,J. Am.Chem.Soc.,116(16),7258-7265(1994).
50 Sakaki,S.,Sumimoto,M.,Fukuhara,M.,Sugimoto,M.,Fujimoto, H.,Matsuzaki,S.,“Why does the rhodium-catalyzed hydrosilylation of alkenes take place through a modified Chalk-Harrod mechanism? A theoretical study”,Organometallics,21(18),3788-3802(2002).

[1]	Suhang Jiang, Lijuan Tan, Yujia Tong, Lijian Shi, Weixing Li. A heterogeneous double chamber electro-Fenton with high production of H₂O₂ using La–CeO₂ modified graphite felt as cathode [J]. Chinese Journal of Chemical Engineering, 2023, 54(2): 98-105.
[2]	Xiaodong Yang, Na Yang, Ziqiang Gong, Feifei Peng, Bin Jiang, Yongli Sun, Luhong Zhang. The superhydrophobic sponge decorated with Ni-Co double layered oxides with thiol modification for continuous oil/water separation [J]. Chinese Journal of Chemical Engineering, 2023, 54(2): 296-305.
[3]	Lu Lv, Min Zhao, Yanan Liu, Yufei He, Dianqing Li. Fabrication of hydrophobic Pd/Al₂O₃-phosphoric acid via P-O-Al bond for liquid hydrogenation reaction [J]. Chinese Journal of Chemical Engineering, 2023, 53(1): 232-242.
[4]	Ting He, Songhong Yu, Jinhui He, Dejian Chen, Jie Li, Hongjun Hu, Xingrui Zhong, Yawei Wang, Zhaohui Wang, Zhaoliang Cui. Membranes for extracorporeal membrane oxygenator (ECMO): History, preparation, modification and mass transfer [J]. Chinese Journal of Chemical Engineering, 2022, 49(9): 46-75.
[5]	Linyang Wang, Qiang Wang, Yongqi Liu, Qiuxiang Yao, Ming Sun, Xiaoxun Ma. Catalytic conversion of asphaltenes to BTXN using metal-loaded modified HZSM-5 [J]. Chinese Journal of Chemical Engineering, 2022, 49(9): 253-264.
[6]	Jinglei Cui, Qian Wang, Jianming Gao, Yanxia Guo, Fangqin Cheng. The selective adsorption of rare earth elements by modified coal fly ash based SBA-15 [J]. Chinese Journal of Chemical Engineering, 2022, 47(7): 155-164.
[7]	Dongqi An, Yuyao Yang, Weixin Zou, Yandi Cai, Qing Tong, Jingfang Sun, Lin Dong. Insight into the promotional mechanism of Cu modification towards wide-temperature NH₃-SCR performance of NbCe catalyst [J]. Chinese Journal of Chemical Engineering, 2022, 50(10): 301-309.
[8]	Chen Zhao, Yahan Ye, Xianfu Chen, Xiaowei Da, Minghui Qiu, Yiqun Fan. Charged modified tight ceramic ultrafiltration membranes for treatment of cationic dye wastewater [J]. Chinese Journal of Chemical Engineering, 2022, 41(1): 267-277.
[9]	Shiyue Li, Shouying Huang, Kai Cai, Ying Li, Jing Lv, Xinbin Ma. Importance of metal location in M-H zeolite for synergistically catalyzing dimethyl ether carbonylation [J]. Chinese Journal of Chemical Engineering, 2022, 41(1): 350-357.
[10]	Jinyan Xi, Kang Meng, Ying Li, Meng Wang, Qiang Liao, Zidong Wei, Minhua Shao, Jianchuan Wang. Performance improvement of ultra-low Pt proton exchange membrane fuel cell by catalyst layer structure optimization [J]. Chinese Journal of Chemical Engineering, 2022, 41(1): 473-479.
[11]	Hang Yao, Yuwei He, Jinrong Ma, Lang Jiang, Jingan Li, Jin Wang, Nan Huang. Recent advances in cardiovascular stent for treatment of in-stent restenosis: Mechanisms and strategies [J]. Chinese Journal of Chemical Engineering, 2021, 37(9): 12-29.
[12]	Chunxiao Zhang, Yingjie Li, Zhiguo Bian, Wan Zhang, Zeyan Wang. Simultaneous CO₂ capture and thermochemical heat storage by modified carbide slag in coupled calcium looping and CaO/Ca(OH)₂ cycles [J]. Chinese Journal of Chemical Engineering, 2021, 36(8): 76-85.
[13]	Qingpeng Cheng, Yunhao Liu, Shuaishuai Lyu, Ye Tian, Qingxiang Ma, Xingang Li. Manipulating metal-support interactions of metal catalysts for Fischer-Tropsch synthesis [J]. Chinese Journal of Chemical Engineering, 2021, 35(7): 220-230.
[14]	Yongqi Liu, Qiuxiang Yao, Ming Sun, Xiaoxun Ma. Selective preparation of light aromatic hydrocarbons from catalytic fast pyrolysis vapors of coal tar asphaltene over transition metal ion modified zeolites [J]. Chinese Journal of Chemical Engineering, 2021, 35(7): 275-287.
[15]	Ting-Ting Liu, Han Xiao, Jian-Hui Xiao, Jian-Jiang Zhong. Impact of oxygen supply on production of terpenoids by microorganisms: State of the art [J]. Chinese Journal of Chemical Engineering, 2021, 29(2): 46-53.