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Expanding the Scope: Monopentafulvene and -Benzofulvene Complexes of Zirconium and Hafnium
Organometallics ( IF 2.5 ) Pub Date : 2018-01-11 00:00:00 , DOI: 10.1021/acs.organomet.7b00832 Malte Fischer 1 , Tim Oswald 1 , Hanna Ebert 1 , Marc Schmidtmann 1 , Rüdiger Beckhaus 1
Organometallics ( IF 2.5 ) Pub Date : 2018-01-11 00:00:00 , DOI: 10.1021/acs.organomet.7b00832 Malte Fischer 1 , Tim Oswald 1 , Hanna Ebert 1 , Marc Schmidtmann 1 , Rüdiger Beckhaus 1
Affiliation
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:
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。
更新日期:2018-01-12
中文翻译:
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。