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Chromium(II) Alkylcyclopentadienyl Complexes with Carbon or Hydride Donor Ligands
Organometallics ( IF 2.5 ) Pub Date : 2021-08-31 , DOI: 10.1021/acs.organomet.1c00159 Igor Smytschkow 1 , Wjatscheslaw Gidt 1 , Yu Sun 1 , Jens Langer 2 , Tobias Böttcher 3 , Lenka Kubíčková 4, 5 , Ondřej Kaman 4 , Helmut Sitzmann 1
Organometallics ( IF 2.5 ) Pub Date : 2021-08-31 , DOI: 10.1021/acs.organomet.1c00159 Igor Smytschkow 1 , Wjatscheslaw Gidt 1 , Yu Sun 1 , Jens Langer 2 , Tobias Böttcher 3 , Lenka Kubíčková 4, 5 , Ondřej Kaman 4 , Helmut Sitzmann 1
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Alkylcyclopentadienylchromium(II) bromide dimers [Cp‴Cr(μ-Br)]2 and [5CpCr(μ-Br)]2 (Cp‴ = tri(tert-butyl)cyclopentadienide, 5Cp = pentaisopropylcyclopentadienide) have been used as starting compounds for replacement of bromide with methyl, hydride, phenyl, phenylacetylide, cyanide, or tetrahydroaluminate anions and afforded dinuclear chromium(II) complexes except for cyanide and tetrahydroaluminate, where tetranuclear products were isolated. Mononuclear chromium complexes have been synthesized by N-heterocyclic carbene addition to the bromide complex or by bromide substitution with a cyclopentadienyl or another alkylcyclopentadienyl ligand. Strong antiferromagnetic coupling with J1,2 = −206 cm–1 of two high-spin Cr(II) central atoms has been found for the dinuclear hydride [Cp‴Cr(μ-H)]2, which was obtained during reactions with isopropylmagnesium chloride via β-hydride elimination and was also found after attempted potassium reduction of the chromium(II) starting compound. Diamagnetic behavior was observed only for the tetranuclear aluminumtetrahydro-tri(tert-butyl)chromate(II).
中文翻译：
铬 (II) 烷基环戊二烯基与碳或氢化物供体配体的配合物
烷基环戊二烯基溴化铬 (II) 二聚体 [Cp‴Cr(μ-Br)] 2和 [ 5 CpCr(μ-Br)] 2 (Cp ‴ = 三(叔丁基)环戊二烯，5 Cp = 五异丙基环戊二烯)用甲基、氢化物、苯基、苯乙炔、氰化物或四氢铝酸盐阴离子代替溴化物的化合物，并提供双核铬 (II) 络合物，但氰化物和四氢铝酸盐除外，其中分离出四核产物。已通过将N-杂环卡宾加成到溴化物络合物或通过溴化物取代环戊二烯基或另一种烷基环戊二烯基配体来合成单核铬络合物。强反铁磁耦合已发现双核氢化物 [Cp‴Cr(μ-H)] 2的两个高自旋 Cr(II) 中心原子的J 1,2 = -206 cm –1，它是在通过 β 与异丙基氯化镁反应期间获得的-氢化物消除，在铬（II）起始化合物尝试钾还原后也发现。仅对四核四氢三（叔丁基）铬酸铝(II)观察到抗磁行为。
更新日期：2021-09-13
中文翻译：
铬 (II) 烷基环戊二烯基与碳或氢化物供体配体的配合物
烷基环戊二烯基溴化铬 (II) 二聚体 [Cp‴Cr(μ-Br)] 2和 [ 5 CpCr(μ-Br)] 2 (Cp ‴ = 三(叔丁基)环戊二烯，5 Cp = 五异丙基环戊二烯)用甲基、氢化物、苯基、苯乙炔、氰化物或四氢铝酸盐阴离子代替溴化物的化合物，并提供双核铬 (II) 络合物，但氰化物和四氢铝酸盐除外，其中分离出四核产物。已通过将N-杂环卡宾加成到溴化物络合物或通过溴化物取代环戊二烯基或另一种烷基环戊二烯基配体来合成单核铬络合物。强反铁磁耦合已发现双核氢化物 [Cp‴Cr(μ-H)] 2的两个高自旋 Cr(II) 中心原子的J 1,2 = -206 cm –1，它是在通过 β 与异丙基氯化镁反应期间获得的-氢化物消除，在铬（II）起始化合物尝试钾还原后也发现。仅对四核四氢三（叔丁基）铬酸铝(II)观察到抗磁行为。
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