六氰铁(II)酸、反式二氰四(甲基异氰化物)铁(II)和反式二氰四(乙基异氰化物)铁(II)与三卤化硼的加合物。红外线和Mössbauer光谱研究

D. Hall, J. Slater, B. Fitzsimmons, K. Wade
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引用次数: 5

摘要

六氰铁(II)酸很容易吸收三氟化硼(但不吸收三氯化硼),形成加合物Fe(CNH)4(CN) 2,2bf3。反式二氰四烷(烷基异氰化物)铁(II)配合物Fe(CNMe)4(CN)2和Fe(CNEt)4(CN)2很容易吸附这些三卤化硼中的任何一种,形成加合物Fe(CNR)4(CN)2,2BX3。这些加合物的红外光谱和穆斯堡尔光谱解释为Fe(CNR)4(CN,BX3)2的结构,其路易斯酸与氰化物基团的氮原子相连。在铁原子上,CNR和CNBX3基团具有相似的π-酸配体性质,但在氰化物拉伸区存在两条适合D4h对称的红外带。
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Adducts of hexacyanoferric(II) acid, trans-dicyanotetrakis(methyl isocyanide)iron(II), and trans-dicyanotetrakis(ethyl isocyanide)iron(II) with boron trihalides. Infrared and Mössbauer spectroscopic studies
Hexacyanoferric(II) acid readily absorbs boron trifluoride (but not boron trichloride) to form the adduct Fe(CNH)4(CN)2,2BF3. The trans-dicyanotetrakis(alkyl isocyanide)iron(II) complexes Fe(CNMe)4(CN)2 and Fe(CNEt)4(CN)2 readily absorb either of these boron trihalides to form adducts Fe(CNR)4(CN)2,2BX3. The i.r. and Mossbauer spectra of these adducts are interpreted in terms of structures Fe(CNR)4(CN,BX3)2 with the Lewis acids linked to the nitrogen atoms of the cyanide group. The spectra are consistent with local octahedral symmetry at iron, indicating the similar π-acid ligand properties of the groups CNR and CNBX3, although in the cyanide stretching region the two i.r. bands appropriate for D4h symmetry are observed.
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