杂环膦亚胺钛配合物的合成及催化乙烯聚合（英文）
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摘要
首先合成单取代和双取代杂环膦化合物R-PPh_2[R=2-吡啶基(3a),2-噻吩基(3b),2-呋喃基(3c)]和Ph_2P-R'-PPh_2[R'=2,6-吡啶基(6a),2,5-噻吩基(6b),2,5-呋喃基(6c)].然后与叠氮三甲基硅烷发生Staudinger反应生成相应的杂环膦亚胺配体R-PPh_2(NSiMe_3)和(Me_3SiN)Ph_2P-R'-PPh2(NSiMe_3).最后与环戊二烯三氯化钛反应脱去三甲基氯硅烷后得到具有烯烃聚合催化活性的杂环膦亚胺钛配合物.所有配合物结构都经过核磁的确认,为了进一步确定配合物分子结构,利用单晶X射线衍射解析了所有钛配合物的晶体结构.在助催化剂甲基铝氧烷(MAO)活化作用下,双钛中心配合物6a~6c比单钛中心类似配合物3a~3c表现出更高的催化乙烯聚合活性,所得聚合物具有较宽分子量分布呈双峰分布,6b在较低聚合温度下就可以制备超高分子量聚乙烯.
Mono-and bisdiphenyl substituted heteroarylphosphines R-PPh_2 [R=2-pyridyl(3a), 2-thienyl(3b) and 2-furyl(3c)] and Ph2 P-R'-PPh_2 [R'=2,6-pyridyl(6a), 2,5-thienyl(6b) and 2,5-furyl(6c)] were synthesized. After Staudinger reaction with Me_3SiN_3, those heteroarylphosphines were converted into the heteroarylphosphinimine ligands, R-PPh_2(NSiMe_3) and(Me_3SiN)Ph_2 P-R''-PPh2(NSiMe_3). The subsequently dehalosilylation reaction with CpTiCl_3 afforded the corresponding Ti heteroarylphosphinimine halfmetallocenes as olefin polymerization catalysts. The structures of all the complexes were determined by means of ~1 H NMR, ~(13)C NMR and 31 P NMR spectroscopic methods and further confirmed by single-crystal X-ray diffraction analysis. When activated with methylaluminoxane(MAO) at a ratio of Al/Ti=600 and under 0.5 MPa of ethylene, these bimetallic Ti phosphinimine complexes displayed a higher catalytic activity compared to the monometallic analogues, but resulted in polymers with bimodal molecular weight distributions. Unexpectedly, 6 b produced ultrahigh Mw polyethylene at lower polymerization temperature.
Mono-and bisdiphenyl substituted heteroarylphosphines R-PPh_2 [R=2-pyridyl(3a), 2-thienyl(3b) and 2-furyl(3c)] and Ph2 P-R'-PPh_2 [R'=2,6-pyridyl(6a), 2,5-thienyl(6b) and 2,5-furyl(6c)] were synthesized. After Staudinger reaction with Me_3SiN_3, those heteroarylphosphines were converted into the heteroarylphosphinimine ligands, R-PPh_2(NSiMe_3) and(Me_3SiN)Ph_2 P-R''-PPh2(NSiMe_3). The subsequently dehalosilylation reaction with CpTiCl_3 afforded the corresponding Ti heteroarylphosphinimine halfmetallocenes as olefin polymerization catalysts. The structures of all the complexes were determined by means of ~1 H NMR, ~(13)C NMR and 31 P NMR spectroscopic methods and further confirmed by single-crystal X-ray diffraction analysis. When activated with methylaluminoxane(MAO) at a ratio of Al/Ti=600 and under 0.5 MPa of ethylene, these bimetallic Ti phosphinimine complexes displayed a higher catalytic activity compared to the monometallic analogues, but resulted in polymers with bimodal molecular weight distributions. Unexpectedly, 6 b produced ultrahigh Mw polyethylene at lower polymerization temperature.
引文
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[12](a)Guo,N.;Li,L.T.;Marks,T.J.J.Am.Chem.Soc.2004,126,6542.(b)Li,H.;Li,L.;Marks,T.J.;Liable-Sands,L.;Rheingold,A.L.J.Am.Chem.Soc.2003,125,10788.(c)Motta,A.;Fragala,I.L.;Marks,T.J.J.Am.Chem.Soc.2009,131,3974.(d)Li,H.;Li,L.;Marks,T.J.Angew.Chem.,Int.Ed.2004,43,4937.(e)Li,L.;Metz,M.V.;Li,H.;Chen,M.-C.;Marks,T.J.;Liable-Sands,L.;Rheingold,A.L.J.Am.Chem.Soc.2002,124,12725.
[13](a)Chahma,M.;Myles,D.J.T.;Hicks,R.G.Can.J.Chem.2005,83,150.(b)Stott,T.L.;Wolf,M.O.J.Phys.Chem.B 2004,108,18815.(c)Reiter,S.A.;Nogai,S.D.;Schmidbaur,H.Dalton Trans.2005,247.(d)Sevcik,R.;Necas,M.;Novosad,Polyhedron 2003,22,1585.
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[15]Stephan,D.W.;Stewart,J.C.;Guérin,F.;Courtenay,S.;Kickham,J.E.;Hollink,E.;Beddie,C.;Hoskin,A.J.;Graham,T.;Wei,P.;Spence,R.E.v.H.;Xu,W.;Koch,L.;Gao,X.;Harrison,D.G.Organometallics 2003,22,1937.
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[17]Chen J.X.;Huang Y.B.;Li Z.S.;Zhang Z.C.;Wei C.X.;Lan T.Y.;Zhang W.J.J.Mol.Catal.A:Chem.2006,259,133.
[18]Xiao X.H.;Sun J.Q.;Li X.;Wang Y.G.;Schumann H.Eur.Polym.J.2007,43,164.