A New Linear Tricobalt Compound with Di(2-pyridyl)amide (dpa) Ligands: Two-Step Spin Crossover of [Co3(dpa)4Cl2][BF4]
作者： Rodolphe Clérac , F. Albert Cotton , Kim R. Dunbar , Tongbu Lu , Carlos A. Murillo
DOI: 10.1021/JA994051B
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摘要: Chemical oxidation of the linear tricobalt compound Co3(dpa)4Cl2 (1) with 1 equiv NOBF4 yields one-electron oxidized species [Co3(dpa)4Cl2]+ (1+), which crystallizes from dichloromethane as a solvate [Co3(dpa)4Cl2][BF4]·2CH2Cl2 (2·2CH2Cl2). The crystal structure 2·xCH2Cl2 (with x varying 1.125 to 2.0) has been determined at 100, 213, and 300 K, showing very little variation an essentially symmetrical arrangement three Co atoms in cation 1+ Co−Co distances 2.3168(8) 2.3289(8) A. terminal cobalt axial chloride are 2.350(1) 2.376(1) A 100 K. maintains its ambient temperature (300 K) only slight lengthening (0.01−0.02 A) Co−N distances. Temperature studies magnetic properties for 2 both solution solid state have revealed spin-crossover behavior occurring two gradual steps, indicating that exhibits diamagnetic ground thermally accessible triplet quintet spin...
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