[해외논문]Di-μ-olato dinuclear copper(II) compounds. The structure of bis-μ-O-[(4,6,6-trimethyl-9-(pyridin-2-yl)-3,7-diazanon-3-en-1-olato)copper(II)] perchlorate
Preparations are reported for blue-green[{Cu(pyen)(eto)}2](ClO4)2[pyen is 2-(2-aminoethyl)pyridine, eto- isdeprotonated 2-aminoethanol] and of green[{Cu(pyaceto)}2](ClO4)2,formed by reaction of this compound with acetone[pyaceto- is deprotonated4,6,6-trimethyl-9-(pyridin-2-yl)-3,7-diazanon-3-en-1-o...
Preparations are reported for blue-green[{Cu(pyen)(eto)}2](ClO4)2[pyen is 2-(2-aminoethyl)pyridine, eto- isdeprotonated 2-aminoethanol] and of green[{Cu(pyaceto)}2](ClO4)2,formed by reaction of this compound with acetone[pyaceto- is deprotonated4,6,6-trimethyl-9-(pyridin-2-yl)-3,7-diazanon-3-en-1-ol]. The structureof[{Cu(pyaceto)}2](ClO4)2shows a unit cell containing two independent, but closely similar,centrosymmetrical dinuclear diolato-bridged cations. The copper(II) ions arein square pyramidal coordination, with the two bridging oxygen atoms, and theimine and secondary amine nitrogen atoms in the basal plane, with the pyridinenitrogen atom more weakly coordinated axially. Mean dimensions for the twocations are Cu-Cu# 2.99, Cu-Nbasal 2.01,Cu-O 1.96, Cu-Naxial 2.24 Å,O-Cu-O# 99, Cu-O-Cu# 81, C-O-Cu110, C-O-Cu# 130˚[C30H46Cl2Cu2N6O10,monoclinic, space group P21/n, a 13.487(1),b 13.356(1), c 20.921(2) Å,β 103.235(3)˚, R1 = 0.0516 for 4694reflections]. Magnetic susceptibilities (100-300 K) showantiferromagnetic spin coupling for[{Cu(pyaceto)}2](ClO4)2and[{Cu(pyen)(eto)}2](ClO4)2with singlet-triplet level separation J of-110(10) and -65(10) cm-1,respectively, indicating that[{Cu(pyen)(eto)}2](ClO4)2also has a dinuclear structure.
Preparations are reported for blue-green[{Cu(pyen)(eto)}2](ClO4)2[pyen is 2-(2-aminoethyl)pyridine, eto- isdeprotonated 2-aminoethanol] and of green[{Cu(pyaceto)}2](ClO4)2,formed by reaction of this compound with acetone[pyaceto- is deprotonated4,6,6-trimethyl-9-(pyridin-2-yl)-3,7-diazanon-3-en-1-ol]. The structureof[{Cu(pyaceto)}2](ClO4)2shows a unit cell containing two independent, but closely similar,centrosymmetrical dinuclear diolato-bridged cations. The copper(II) ions arein square pyramidal coordination, with the two bridging oxygen atoms, and theimine and secondary amine nitrogen atoms in the basal plane, with the pyridinenitrogen atom more weakly coordinated axially. Mean dimensions for the twocations are Cu-Cu# 2.99, Cu-Nbasal 2.01,Cu-O 1.96, Cu-Naxial 2.24 Å,O-Cu-O# 99, Cu-O-Cu# 81, C-O-Cu110, C-O-Cu# 130˚[C30H46Cl2Cu2N6O10,monoclinic, space group P21/n, a 13.487(1),b 13.356(1), c 20.921(2) Å,β 103.235(3)˚, R1 = 0.0516 for 4694reflections]. Magnetic susceptibilities (100-300 K) showantiferromagnetic spin coupling for[{Cu(pyaceto)}2](ClO4)2and[{Cu(pyen)(eto)}2](ClO4)2with singlet-triplet level separation J of-110(10) and -65(10) cm-1,respectively, indicating that[{Cu(pyen)(eto)}2](ClO4)2also has a dinuclear structure.
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