Transition Metal Complexes Containing an Optically Active Macrocyclic Ligand. Manganese(III), Nickel(II), and Copper(II)

Philip S. Bryan; James C. Dabrowiak

doi:10.1021/ic50144a017

Transition Metal Complexes Containing an Optically Active Macrocyclic Ligand. Manganese(III), Nickel(II), and Copper(II)

Philip S. Bryan, James C. Dabrowiak

Department of Chemistry

Research output: Contribution to journal › Article › peer-review

25 Scopus citations

Abstract

The synthetic macrocyclic ligand rac-5,7,7,12,12,14-hexamethy 1-1,4,8,11 -tetraazacyclotetradecane (rac-5,14-[14]aneN₄) has been resolved via its nickel(ll) complex. The optically active ligand has been removed from Ni(II) and transferred to copper(II) and manganese(III). A circular dichroism analysis of (+)[Mn((–)5,14-[14]aneN₄)X₂]PF₆, where X^- is Cl^- or Br^-, has been very useful in interpreting the electronic spectrum of this tetragonally distorted high-spin d⁴ system. The macrocyclic crystal field (10Dq) for Mn(III) as measured by the position of the ⁵B_1g → ⁵B_2g electronic transition was found to be about 23 kK.

Original language	English (US)
Pages (from-to)	299-302
Number of pages	4
Journal	Inorganic Chemistry
Volume	14
Issue number	2
DOIs	https://doi.org/10.1021/ic50144a017
State	Published - Feb 1 1975

ASJC Scopus subject areas

Physical and Theoretical Chemistry
Inorganic Chemistry

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title = "Transition Metal Complexes Containing an Optically Active Macrocyclic Ligand. Manganese(III), Nickel(II), and Copper(II)",

abstract = "The synthetic macrocyclic ligand rac-5,7,7,12,12,14-hexamethy 1-1,4,8,11 -tetraazacyclotetradecane (rac-5,14-[14]aneN4) has been resolved via its nickel(ll) complex. The optically active ligand has been removed from Ni(II) and transferred to copper(II) and manganese(III). A circular dichroism analysis of (+)[Mn((–)5,14-[14]aneN4)X2]PF6, where X- is Cl- or Br-, has been very useful in interpreting the electronic spectrum of this tetragonally distorted high-spin d4 system. The macrocyclic crystal field (10Dq) for Mn(III) as measured by the position of the 5B1g → 5B2g electronic transition was found to be about 23 kK.",

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N2 - The synthetic macrocyclic ligand rac-5,7,7,12,12,14-hexamethy 1-1,4,8,11 -tetraazacyclotetradecane (rac-5,14-[14]aneN4) has been resolved via its nickel(ll) complex. The optically active ligand has been removed from Ni(II) and transferred to copper(II) and manganese(III). A circular dichroism analysis of (+)[Mn((–)5,14-[14]aneN4)X2]PF6, where X- is Cl- or Br-, has been very useful in interpreting the electronic spectrum of this tetragonally distorted high-spin d4 system. The macrocyclic crystal field (10Dq) for Mn(III) as measured by the position of the 5B1g → 5B2g electronic transition was found to be about 23 kK.

AB - The synthetic macrocyclic ligand rac-5,7,7,12,12,14-hexamethy 1-1,4,8,11 -tetraazacyclotetradecane (rac-5,14-[14]aneN4) has been resolved via its nickel(ll) complex. The optically active ligand has been removed from Ni(II) and transferred to copper(II) and manganese(III). A circular dichroism analysis of (+)[Mn((–)5,14-[14]aneN4)X2]PF6, where X- is Cl- or Br-, has been very useful in interpreting the electronic spectrum of this tetragonally distorted high-spin d4 system. The macrocyclic crystal field (10Dq) for Mn(III) as measured by the position of the 5B1g → 5B2g electronic transition was found to be about 23 kK.

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