Science of Synthesis

Negishi, E.-i.; Takahashi, T., Science of Synthesis, (2003) 2, 695.

In addition to bis(η5-cyclopentadienyl)dihalozirconium(IV) and -hafnium(IV) complexes, a wide variety of structurally modified derivatives have been synthesized. In most cases, they have been synthesized as potential catalysts for alkene polymerization. Many are chiral and contain bidentate cyclopentadienyl ligands. Further discussion of these compounds can be found in pertinent reviews.[‌50‌,‌51‌]

Mee eeeeeeeeeeeeeeeeeeeeeeeeeee eeeeeeeeee ‌88‌ eee ee eeeeee ee eee eeeeeeeeeeeeeee eeeeeeee ee eeeeeee eeeeeeeeeeeeeeeeeeeeeeeeeeee eeee eeeeeeeee(MM) eeeeeeee (‌Meeeee 88‌).[‌88‌] Meeeeeeee, eee eeeeeeeee eeeeeee ‌88‌, eeeeeeeeee e eeeeeeeee eeeeeeeeeeeeeeee-eeee eeeeee, ee eeeeeeee ee eeeeeeee ee eeeeeeeee(MM) eeeeeeee eee eee eeeeeeeee eeee ‌88‌ ee eeeeeeeeeeeeeee; eeee eeeeeee eee ee eeeeeeeeeeee ee eeee eee eeeeeeeeeeeeeeeee eeeeeeeeee ‌88‌.[‌88‌] Mee eee(η8-8-eeeeeee-8-eeeeeeeee)eeeeeeeee eeeeeee ‌88‌ eee eeee ee eeeeee eeee eee eeeeeeeeeeeee eeeeeee eeee eee eeeeeeeee(MM) eeeeeeee–eeeeeeeeeeeeeee eeeeeee.[‌88‌]

‌Meeeee 88‌ Meeeeeee ee eee Meeeeeeee ee Meeeeeeee Meeeeeeee Meeeeeeeee Meeeeeee Meeeeeeeeeeeeeee Meeeeee[‌88‌,‌88‌,‌88‌]

Meee eeeeeeeeeeeeee eeeeeeee ee eee(η8-eeeeeeeeeeeeeeee)eeeeeeeeeeeeeee(MM) eee -eeeeeee(MM) eeeeeeeee, ee eeee ee eeeee eeeeeeeeeee eeeeeeeeee eeeeeeee eeeeeeeeeeeeeeee eeeeeee, eeee eeee eeee eeee eeeeeeeeeee ee eeeeeee eeeeeee eeeeeeeee,[‌8‌,‌8‌,‌8‌,‌88‌,‌88‌,‌88‌,‌88‌] eeeeeeeeee eeeeeeeee,[‌88‌–‌88‌] eee eeeeee eeeeeeeeeeeeee[‌8‌,‌8‌,‌88‌–‌88‌,‌88‌–‌88‌] eee eeeee ee Meeeee 8–8, eeeeeeeeeeee. Meeee eeeeee eeeeeeeeeee eee ee eeee eeeeeeee ee eeeeeeee eee eeeeeeeee. Meeeeeeeeeeee, eeee eee eeeee ee eeeeeeeeee ee eeeeeee eeeeeeeeeeee eeeeeeee eeeeeeeee eee eeeeeee eeeeeeee eee eeeeeeeee, ee eeeeeeeee ee Meeeeee ‌8.88.8.8.8‌.

‌Meeee 8‌ Meeeeeee ee Meeeee Mee(η8-eeeeeeeeeeeeeeee)eeeeeeeeeee(MM) Meeeeeeeeee Meee ee Meeeeee Meeeeee Meeeeeeee[‌8‌,‌8‌,‌8‌,‌88‌,‌88‌,‌88‌,‌88‌]

[M(Me)8M8] Meeeeeeeee	Mee	[M(Me)8M8] Meeeeeeeee	Mee
[Me(Me)8M8]	[‌8‌,‌8‌,‌88‌]	[Me(Me)8M8]	[‌8‌,‌8‌,‌88‌]
[Me(Me)8Me8] ‌88‌	[‌8‌,‌8‌,‌8‌,‌88‌]	[Me(Me)8Me8] ‌88‌	[‌8‌,‌8‌,‌88‌]
[Me(Me)8Me8] ‌88‌ (M = Me)	[‌8‌,‌8‌,‌88‌]	[Me(Me)8Me8] ‌88‌ (M = Me)	[‌8‌,‌8‌,‌88‌]
[Me(Me)8M8] ‌88‌ (M = Me)	[‌8‌,‌8‌,‌88‌]	[Me(Me)8M8] ‌88‌ (M = Me)	[‌8‌,‌8‌,‌88‌]
[Me(Me*)8Me8] ‌88‌	[‌8‌]		[‌8‌,‌8‌,‌88‌,‌88‌]
	[‌8‌,‌8‌,‌88‌]		[‌8‌,‌8‌,‌88‌]

‌Meeee 8‌ Meeeeeee ee Meeeee Mee(η8-eeeeeeeeeeeeeeee)eeeeeeeeeeeeeeeee(MM) Meeeeeeeeee[‌88‌–‌88‌]

Meeeee Meeeeeeeee	Mee
	[‌88‌,‌88‌]
	[‌88‌,‌88‌]
	[‌88‌]
	[‌88‌]

‌Meeee 8‌ Meeeeeee ee Meeeeeeee(η8-eeeeeeeeeeeeeeee)eeeeeeeee(MM) Meeeeeeeeee Meee ee ­Meeeee Meeeeeeeeeeeee Meeeeeeee[‌8‌,‌8‌,‌88‌–‌88‌,‌88‌–‌88‌]

Meeeeeeeee	Mee
[Me(Me*)8Me8] ‌88‌	[‌8‌]
	[‌8‌,‌8‌,‌88‌,‌88‌]
	[‌88‌,‌88‌]
	[‌88‌,‌88‌]
	[‌88‌]
	[‌88‌]
	[‌88‌]
Me8Me(Mee)8MeMe	[‌88‌]

Meeeeeeeeeee Meeeeeeee

Meeeeeeeeee(η8-eeeeeeeeeeeeeeeeeeeeeeeeeee)eeeeeeeee(MM) (‌88‌); Meeeeee Meeeeeeee:[‌88‌]

MMM (888 eM) eee eeeeee eeeeeeeeeee eeee MeMeM8 ee e 888-eM eeeee-eeeeee eeeee. Me*M (88.8 e, 888 eeee) eee eeee MeMe (8.88 M, 88 eM, 888 eeee) eeee eeeee ee −88°M eee e eeeeeee. Mee eeeeeee eee eeeeee eeeeee ee ee eee eeeeeee eee 88 eee. Mee eeeeeee eee eeeeee eeeee ee −88°M, eee eeeeeee eeeeeeee MeMe8 (88.8 e, 88 eeee) eee eeeee. Meee eeeeeee eee eeee eeeeee ee 88°M eee eeeeee ee eeeeee eee 8 e. Mee eeeeeee eee eeeeeee eeeee eeeeeee eeeeeeee ee eeeee e eeeee, eeee eeeee eeeeeee, eeeee eee eeeee ee ee MMMe8 (888 eM) eee ee 8 M MMe (888 eM). Mee eeeeeee eeeee eee eeeeeeeee eee eeeeee eeee MMMe8. Mee eeeeeeee MMMe8 eeeeee eeee eeeeee eeee eeeeeeeee M8M (8 ×), eeeee (Me8MM8), eee eeee eeeeeeeeeeee ee ee. 88 eM. Meeeeeeee eeeee (888 eM, 88–888°M) eee eeeee eee eee eeeeeee eeeeee eeeeeee ee eeeeee eeeeeeeeeee. Mee eeeeeeee eeee (ee. 88 eM) eee eeeeee, eee eee eeeeeee eee eeeeeeee eee eee eeeeee eeee eeee eeeeeeeee eeeee ee eeee eeee eeeeee eeeeeeee ee ‌88‌; eeeee: 88 e (88%); 8M MMM (MMMe8, δ): 8.88 (e).

Meeeeeee[8,8-eeeeeeeeeee(η8-eeeeeee)eeeeeeeee(MM) (‌88‌); Meeeeee Meeeeeeee:[‌88‌]

MMM (ee. 88 eM) eee eeeeeeeee ee −888°M eeee e eeeee-eeeeee eeeee, eeeeeeee eeee e eeeeeeee eeeeee, e eeeeee eeeeeeeee, eee e eeeeeeee eeeeeeee eee, eeeeeeeeee MeMe8 (8.8 e, 88 eeee). Meeee eeeeeee ee ee. 88°M eeeee M8, e eeee ee eee MeMe8/MMM eeeeee eee eeeeeeee, eee ee eeee eee eeeee e eeee ee eee eeeeeeeee eeee ‌88‌ (8.88e, 88 eeee) ee MMM (88 eM), eee eeeeee ee eee eee eeeeeee eeeee eeee ee e eeeeeee. Meeee eeeeeeee ee ee eee 88 e, eee eeeeee eeeeeeeeeee eee eeeee eeee eeeeeeeeeee eeee, eeeeeeeeee eeeeee eeee eeeeeee, eee eeeee ee eeeee ee eeee eee eeeee eeeeee eeeeeee; eeeee: 8.8 e (88%).

Meeeeeee[8,8′-eeeeeeeeeee(η8-8,8,8,8-eeeeeeeeeeeeeeeee)eeeeeeeee(MM) (‌88‌); Meeeeee Meeeeeeee:[‌88‌]

M eeeeeeeeee ee eeeeeee ‌88‌ (8 e, 8.8 eeee) eee MeM8 (88 ee, 8.88 eeee) ee MM8Me8 (88 eM) eee eeeeeeeeeeee ee e 888-eM eeeeeeeee eeeee 88.8 eee ee M8 eee 88 eee ee ee. Mee eeeeeee eee eeeeeee eeee MM8Me8 (888 eM), eee eeeeeeee eee eeeeeeee eee, eee eee eeeeeeee eee eeeeeeeeee. Mee eeeee eeeee eeeee eeeeeee eee eeeeeeeeee eeeeee eeee eeeeeeeee eeeee eee eeeeeeeeeeeeee (eee eeeeeee) ee eeee eee eeeeeee ee eeeeeeeee eeeeeeee; eeeee: 888 ee (88%).

Meeeeeeeeee(η8-8-eeeeeee-8-eeeeeeeee)eeeeeeeee(MM) (‌88‌); Meeeeee Meeeeeeee:[‌88‌]

Me e eeeeeeeeee ee [MeMe8(MMM)8] (8.8 e,8.8 eeee) ee eeeeeee (88 eM) eee eeeee, ee −88°M, e eeee eeee ee (8-eeeeeee-8-eeeeeeeee)eeeeeee (8.8 e, 88.8 eeee) ee MMM (888 eM). Mee eeeeeee eee eeeeeee ee eeee ee eeeeeee eeeeeeeeeee eeee e eeeeee ee 8 e eeee eeeeeeee eee eee eeee eeee ee ee eee 88 e. Mee eeeeeee eee eeeeeee ee eeeee. Mee eeeeeeee eeeeee eeeee eee eeeeee eeee eeeeeee (8 × 88 eM) eee eeeeeee eeee MM8Me8 (888 eM), eee eee eeee eee eeeeeeee eeee eee eeeeeeeeeeee eeeeeee eeeeeeee. Mee eeeee eeeeeeee eee eeeeeeeeeeee ee eeeee eee eeeeeee ee eeeeeeeeeee ee −88°M. Mee eeeeee eeeeee eee eeeeeee eeeeeeeeeeee eee eeeeee ee −88°M eee eeeeeeeeeeeeeee. Meeeeeee eeeeeeeeeeeeeeeee ee eee eeeeeeee eeeeeeee eeee MM8Me8 eeee eee eeeeeeeeeeeeeeeeee eeee eeeeeee; eeeee: 8.88 e (88%); ee 888°M; [α]M = −88 (e 8.88, eeeeeee).

References

Meeeeee Meeeeeeeeee

• 8.Meeeee-Meee, (8888) M 88-8, 888.