(κ-N,N(py)2-1,3-dipyridyl-2-azaallyl)CrN(TMS)2 | 1191437-63-4

• 分子结构分类: 有机化合物 - 有机杂环化合物 - 吡啶及其衍生物
• 英文名称: (κ-N,N(py)2-1,3-dipyridyl-2-azaallyl)CrN(TMS)2
• 英文别名: (smif)CrN(TMS)2
• CAS: 1191437-63-4
• 化学式: C₁₈H₂₈CrN₄Si₂
• 分子量: 408.614
• InChiKey: CHVHWSKGIQEUDY-IGUOPLJTSA-N

计算性质

• 辛醇/水分配系数(LogP)：
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• 重原子数：
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• 可旋转键数：
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• 环数：
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• sp3杂化的碳原子比例：
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• 拓扑面积：
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• 氢给体数：
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• 氢受体数：
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反应信息

• 作为产物：
  描述：

  sodium hexamethyldisilazane 以 四氢呋喃 、 乙醚 为溶剂， 生成 (κ-N,N(py)2-1,3-dipyridyl-2-azaallyl)CrN(TMS)2
  参考文献：
  名称：

  Aryl-Containing Chelates and Amine Debenzylation to Afford 1,3-Di-2-pyridyl-2-azaallyl (smif): Structures of {κ-C,N,N^py₂-(2-pyridylmethyl)₂N(CH₂(4-^tBu-phenyl-2-yl))}FeBr and (smif)CrN(TMS)₂

  摘要：

  Aryl-bromide ligand precursors have been prepared with the potential to afford tetradentate chelates (2-pyridylmethyl)(3-x)N(CH2-2-Aryl)(x)(x = 1, 2) containing metal-aryl linkages that promise to impart stronger fields about first row transition metals. Oxidative addition to Ni(COD)(2) afforded two diamagnetic Ni(II) complexes, (kappa-C,N,N-py-(2-pyridylmethyl)N(CH2(4-Bu-t-phenyl-2-yl))(CH2(4-Bu-t-phenyl-2-Br))}NiBr (1-Ni) and {(kappa-C,N,N-2(py)-(2-pyridylmethyl)(2)N(CH2(4-Bu-t-phenyl-2-yl))}NiBr (2-Ni) in 96% and 67% yield, respectively. Extending these synthetic efforts to iron provided {kappa-C,N,N-2(py)-(2-pyridylmethyl)(2)N(CH2(4-Bu-t-phenyl-2-yl))}FeBr (2-Fe, X-ray) in 91% yield via reduction of an adduct, {kappa-N,N-2(py)-(2-pyridylmethyl)(2)N(CH2(4-Bu-t-phenyl-2-Br))}FeBr2 (3-Fe). 5-Coordinate 2-Fe possessed a pseudo-tbp structure, and SQUID magnetometry showed it to be S = 2 with significant zero field splitting (ZFS). 2Fe was initially prepared via oxidative addition to Fe{N(TMS)(2))(2)(THF) upon disproportionation to "Fe(0)" and 2 Fe{N(TMS)(2)}(3), but when this approach was attempted with Cr{N(TMS)(2)}(2)(THF)(2), the azaallyl complex {kappa-N,N-2(py)-1,3-dipyridyl-2-azaallyl}CrN(TMS)(2) ((smif)CrN(TMS)(2), 4-Cr, X-ray), formed instead (>50%) via amine debenzylation. An alternative route consisting of addition of 1,3-di-2-pyridyl-2-azapropene to Cr{N(TMS)(2)}(2)(THF)(2) afforded 4-Cr in 74% yield. Pseudo-square planar 4-Cr was also S = 2 (SQUID) with marked ZFS. The dipyridylazaallyl ligand "smif" imparts a remarkable optical density to 4-Cr via intraligand bands at 675 nm (epsilon similar to 15 000 M(-1)cm(-1)) and 396 nm (epsilon similar to 27 000 M(-1)cm(-1)). The effective fields of the chelate complexes are discussed, and a comparison of smif to isoelectronic NHC ligands is given.

  DOI：

  10.1021/ic901329z