The reaction of Cp*MCl₃ (M = Zr, Zr1; M = Hf, Hf1) with the reducing agent Na/Hg (20% Na) and with sterically encumbered pentafulvenes adamantylidenepentafulvene AdFv, 6,6′-di-p-tolylpentafulvene pTol₂Fv, and benzofulvenes adamantylidenebenzofulvene AdBzFv, 10,10′-di-p-tolylbenzofulvene pTol₂BzFv, and 10,10′-diphenylbenzofulvene Ph₂BzFv yielded the corresponding pentafulvene complexes (η⁵-pentamethylcyclopentadienyl)metal(η⁵:η¹-pentafulvene)chloride (Zr2a,b, Hf2a,b) and benzofulvene complexes (η⁵-pentamethylcyclopentadienyl)metal(η⁵:η¹-benzofulvene)chloride (Zr3a–c, Hf3a). This reductive complexation approach can be used in a multigram scale and mostly very good yields (up to 92%). In addition to NMR spectroscopic analyses, the pentafulvene complex Zr2b and benzofulvene complex Zr3b were characterized by X-ray crystallography, showing mainly the π–η⁵:σ–η¹ dianionic bonding mode together with slight influence of the π–η²:π–η³:σ–η¹ bonding mode. By use of the prochiral benzofulvenes the corresponding complexes Zr3a–c and Hf3a are furthermore obtained in a diastereoselective manner.

中文翻译：

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扩大范围：锆和Ha的单五烯富烯和-苯甲富烯配合物

Cp * MCl ₃（M = Zr，Zr1 ; M = Hf，Hf1）与还原剂Na / Hg（20％Na）以及与空间受限的五烯丙基戊二烯基亚戊基戊烯基AdFv，6,6' - di - p-对甲苯基戊烯基戊烯的反应p托尔₂的Fv，和benzofulvenes adamantylidenebenzofulvene AdBzFv，10,10'-二- p -tolylbenzofulvene p托尔₂ BzFv，和10,10'- diphenylbenzofulvene博士₂ BzFv得到相应pentafulvene络合物（η ⁵ -五甲基）金属（η ⁵：η¹ -pentafulvene）氯化物（Zr2a，b，Hf2a，b）和benzofulvene络合物（η ⁵ -五甲基）金属（η ⁵：η ¹ -benzofulvene）氯化物（Zr3a - Ç，Hf3a）。这种还原络合方法可用于多克规模，且收率大多很高（高达92％）。除了NMR光谱分析外，还通过X射线晶体学对五氟甲醚络合物Zr2b和苯并呋喃酮络合物Zr3b进行了表征，主要显示了π–η ⁵：σ–η ^1。双键键合模式以及π–η ²：π–η ³：σ–η ¹键合模式的轻微影响。通过使用前手性苯并富勒烯酮，还可以以非对映选择性的方式获得相应的配合物Zr3a – c和Hf3a。