Phosphazene-Functionalized Cyclopentadienyl and Its Derivatives Ligated Rare-Earth Metal Alkyl Complexes: Synthesis, Structures, and Catalysis on Ethylene Polymerization

Abstract

Treatment of Ln(CH 2 SiMe 3 ) 3 (thf) 2 (Ln = Sc, Y, and Lu) with 1 equiv of CpPN-type ligands C 5 H 4 ═PPh 2 –NH–C 6 H 3 R 2 (R = Me, L 1 (Me); R = i Pr, L 1 ( i Pr) ) at room temperature readily generated the corresponding CpPN-type bis(alkyl) complexes 1 and 2a – 2c . Addition of 3 equiv of LiCH 2 SiMe 3 to a mixture of L 1 ( i Pr) and LnCl 3 (thf) 2 (Ln = Sm and Nd) also afforded the CpPN-type bis(alkyl) complexes 2d and 2e . The Cp moiety bonds to the central metal in a classical η 5 mode in all CpPN-type complexes 1 and 2 . In contrast, the Cp Me PN-type ligands C 5 Me 4 H–PPh 2 ═N–C 6 H 3 R 2 (R = Me, L 2 (Me); R = i Pr, L 2 ( i Pr) ) behaved differently. L 2 (Me) did not react with Sc(CH 2 SiMe 3 ) 3 (thf) 2 . Similarly, L 2 ( i Pr) was also inert to Sc(CH 2 SiMe 3 ) 3 (thf) 2 even at 50 °C. When the central metal was changed to yttrium, however, the equimolar reaction between Y(CH 2 SiMe 3 ) 3 (thf) 2 and L 2 ( i Pr) in the presence of LiCl afforded two bis(alkyl) complexes 3a and 3b . In the main product 3a, [C 5 HMe 3 (η 3 -CH 2 )–PPh 2 ═N–C 6 H 3 i Pr 2 ]Y(CH 2 SiMe 3 ) 2 (thf), the ligand bonds to the Y 3+ ion in a rare η 3 -allyl/κ-N mode, whereas in 3b, ( C 5 Me 4 –PPh 2 ═N–C 6 H 3 i Pr 2 )Y(CH 2 SiMe 3 ) 2 (LiCl)(thf), the Cp ring coordinates to the Y 3+ ion in an η 5 mode, and a LiCl unit is located between the Y 3+ ion and the nitrogen atom. When the central metal was changed to lutetium, a bis(alkyl) complex 4a, [C 5 HMe 3 (η 3 -CH 2 )–PPh 2 ═N–C 6 H 3 i Pr 2 ]Lu(CH 2 SiMe 3 ) 2 (thf), and a bis(alkyl) complex 4b, (C 5 Me 4 –PPh 2 ═N–C 6 H 3 i Pr 2 )Lu(CH 2 SiMe 3 ) 2, were isolated. The protonolysis reaction of the IndPN-type ligands C 9 H 7 –PPh 2 ═N–C 6 H 3 R 2 (R = Me, L 3 (Me); R = Et, L 3 (Et); R = i Pr, L 3 ( i Pr) ) with Ln(CH 2 SiMe 3 ) 3 (thf) 2 (Ln = Sc, Y, and Lu) generated the IndPN-type bis(alkyl) complexes 5a – 5c, 6, and 7a – 7c, selectively, where the Ind moiety tends to adopt an η 3 -bonding fashion. The more bulky FluPN-type ligands C 13 H 9 –PPh 2 ═N–C 6 H 4 R (R = H, L 4 (H); R = Me, L 4 (Me) ) were treated with Ln(CH 2 SiMe 3 ) 3 (thf) 2 (Ln = Sc and Lu) to afford the FluPN-type bis(alkyl) complexes 8 and 9a and 9b, where the Flu moiety has a rare η 1 -bonding mode. Complexes 1 – 9 were fully characterized by 1 H, 13 C, and 31 P NMR; X-ray; and elemental analyses. Upon activation with AlR 3 and [Ph 3 C][B(C 6 F 5 ) 4 ], the scandium complexes showed good to high catalytic activity for ethylene polymerization. The effects of the sterics and electronics of the ligand, the loading and the type of AlR 3, the polymerization temperature, and the polymerization time on the catalytic activity were also discussed.