Y(2,6-Et₂C₆H₃NCHN-2,6-Et₂C₆H₃)[N(SiHMe₂)₂]₂(thf) | 1418145-54-6

• 分子结构分类: 有机化合物 - 苯类化合物 - 苯和取代衍生物
• 英文名称: Y(2,6-Et₂C₆H₃NCHN-2,6-Et₂C₆H₃)[N(SiHMe₂)₂]₂(thf)
• CAS: 1418145-54-6
• 化学式: C₃₃H₆₃N₄OSi₄Y
• 分子量: 733.137
• InChiKey: GCHIOSTWWQDOLZ-UHFFFAOYSA-N

反应信息

• 作为反应物：
  描述：

  Y(2,6-Et₂C₆H₃NCHN-2,6-Et₂C₆H₃)[N(SiHMe₂)₂]₂(thf) 、 三甲基铝 以 氘代苯 为溶剂， 反应 1.0h， 生成 Y(2,6-Et₂C₆H₃NCHN-2,6-Et₂C₆H₃)(AlMe₄)₂
  参考文献：
  名称：

  C–H Bond Activation and Isoprene Polymerization by Rare-Earth-Metal Tetramethylaluminate Complexes Bearing Formamidinato N-Ancillary Ligands

  摘要：

  The bimetallic formamidinate complexes Ln(Form)(AlMe4)(2) (Ln = Y, Form (ArNCHNAr) = Et Form (Ar = 2,6-Et2C6H3), MesForm (Ar = 2,4,6-Me3C6H2), DippForm (Ar = 2,6-iPr(2)C(6)H(3)), tBuForrn (Ar = 2-tBuC(6)H(4)); Ln = La, Form = DippForm, tBuForm) were obtained in high yield by protonolysis reactions between formamidines (FormH) and homoleptic rare-earth-metal tetramethylaluminates Ln(AlMe4)(3). Y(Form)(AlMe4)(2) (Form = Et Form, DippForm) were also prepared by treatment of Y(Form) [N(SiHMe2)(2)](2)(thf) with trimethylaluminum after the former were prepared by the protonolysis of Y[N(SiHMe2)(2)](3)(thf)(2) complexes with EtFormH or DippFormH. The monomeric six-coordinate complexes Ln(Form)(AlMe4)(2) (Ln = Y, Form = Et Form, MesForm, DippForm, tBuForm; Ln = La, Form = DippForm, tBuForm) show similar molecular structures with distorted-octahedral geometry and bidentate (N,N') Form and AlMe4 ligands. The complex [La(EtFormAlMe(3))(AlMe4)(2)](C7H8)(1.5) from a protonolysis reaction between La(AlMe4)(3) and EtFormH has the Et Form ligand adopting a configuration in which one nitrogen and one aryl substituent are coordinated to the eight coordinate lanthanum center in an eta(1)(N):eta(6)(arene) manner. From the reaction of La(AlMe4)(3) with MesFormH, C-H bond activation of an o-methyl group of the mesityl moiety occurred, yielding [La{eta(1)(N)eta(6)(Ar)-Me(2)CH(2)FormAlMe(3)}(AlMe3)(AlMe4)][La(Me(2)CH(2)FormAlMe(3))(AlMe3)(AlMe4)](C6H4)(1.5) (Me(2)CH(2)Form = MesForm-H(o-Me)), in which two linkage isomers of Me(2)CH(2)Form were observed. Investigations were carried out on the compounds [Ln(Form)(AlMe4)(2)] (Ln = Y, La; Form = EtForm, DippForm) as precatalysts activated by [Ph3C][B(C6F5)(4)] or [PhNMe2H][B(C6F5)(4)] in isoprene polymerization. While the lanthanum complexes showed narrower molecular weight distributions (PDI < 1.2), a stereodirecting role was evidenced for the cocatalysts (trityl borate, maximum 87% trans-1,4-selectivity; anilinium borate, maximum 82% cis-1,4-selectivity).

  DOI：

  10.1021/om301010m
• 作为产物：
  描述：

  N,N'-bis(2,6-diethylphenyl)formamidine 、 Y[N(SiHMe₂)₂]₃(thf)₂ 以 正己烷 为溶剂， 反应 16.0h， 以38%的产率得到Y(2,6-Et₂C₆H₃NCHN-2,6-Et₂C₆H₃)[N(SiHMe₂)₂]₂(thf)
  参考文献：
  名称：

  C–H Bond Activation and Isoprene Polymerization by Rare-Earth-Metal Tetramethylaluminate Complexes Bearing Formamidinato N-Ancillary Ligands

  摘要：

  The bimetallic formamidinate complexes Ln(Form)(AlMe4)(2) (Ln = Y, Form (ArNCHNAr) = Et Form (Ar = 2,6-Et2C6H3), MesForm (Ar = 2,4,6-Me3C6H2), DippForm (Ar = 2,6-iPr(2)C(6)H(3)), tBuForrn (Ar = 2-tBuC(6)H(4)); Ln = La, Form = DippForm, tBuForm) were obtained in high yield by protonolysis reactions between formamidines (FormH) and homoleptic rare-earth-metal tetramethylaluminates Ln(AlMe4)(3). Y(Form)(AlMe4)(2) (Form = Et Form, DippForm) were also prepared by treatment of Y(Form) [N(SiHMe2)(2)](2)(thf) with trimethylaluminum after the former were prepared by the protonolysis of Y[N(SiHMe2)(2)](3)(thf)(2) complexes with EtFormH or DippFormH. The monomeric six-coordinate complexes Ln(Form)(AlMe4)(2) (Ln = Y, Form = Et Form, MesForm, DippForm, tBuForm; Ln = La, Form = DippForm, tBuForm) show similar molecular structures with distorted-octahedral geometry and bidentate (N,N') Form and AlMe4 ligands. The complex [La(EtFormAlMe(3))(AlMe4)(2)](C7H8)(1.5) from a protonolysis reaction between La(AlMe4)(3) and EtFormH has the Et Form ligand adopting a configuration in which one nitrogen and one aryl substituent are coordinated to the eight coordinate lanthanum center in an eta(1)(N):eta(6)(arene) manner. From the reaction of La(AlMe4)(3) with MesFormH, C-H bond activation of an o-methyl group of the mesityl moiety occurred, yielding [La{eta(1)(N)eta(6)(Ar)-Me(2)CH(2)FormAlMe(3)}(AlMe3)(AlMe4)][La(Me(2)CH(2)FormAlMe(3))(AlMe3)(AlMe4)](C6H4)(1.5) (Me(2)CH(2)Form = MesForm-H(o-Me)), in which two linkage isomers of Me(2)CH(2)Form were observed. Investigations were carried out on the compounds [Ln(Form)(AlMe4)(2)] (Ln = Y, La; Form = EtForm, DippForm) as precatalysts activated by [Ph3C][B(C6F5)(4)] or [PhNMe2H][B(C6F5)(4)] in isoprene polymerization. While the lanthanum complexes showed narrower molecular weight distributions (PDI < 1.2), a stereodirecting role was evidenced for the cocatalysts (trityl borate, maximum 87% trans-1,4-selectivity; anilinium borate, maximum 82% cis-1,4-selectivity).

  DOI：

  10.1021/om301010m