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Crystal structure and spectroscopic characterization of a cobalt(II) tetraazamacrocycle: completing a series of first-row transition-metal complexes

Van Heuvelen, Katherine M. and Lee, Isabell and Arriola, Katherine and Griffin, Rilke and Ye, Christopher and Takase, Michael K. (2017) Crystal structure and spectroscopic characterization of a cobalt(II) tetraazamacrocycle: completing a series of first-row transition-metal complexes. Acta Crystallographica Section C: Structural Chemistry, 73 (8). pp. 620-624. ISSN 2053-2296. doi:10.1107/S2053229617010397.

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The tetraazamacrocyclic ligand 1,4,8,11-tetramethyl-1,4,8,11-tetraazacyclotetra-decane (TMC) has been used to bind a variety of first-row transition metals but to date the crystal structure of the cobalt(II) complex has been missing from this series. The missing cobalt complex chlorido(1,4,8,11-tetramethyl-1,4,8,11-tetraazacyclotetradecane-κ^4N)cobalt(II) chloride dihydrate, [CoCl(C_(14)H_(32)N_4)]Cl·2H_2O or [Co^(II)Cl(TMC)]Cl·2H_2O, crystallizes as a purple crystal. This species adopts a distorted square-pyramidal geometry in which the TMC ligand assumes the trans-I configuration and the chloride ion binds in the syn-methyl pocket of the ligand. The Co^(II) ion adopts an S = 3/2 spin state, as measured by the Evans NMR method, and UV–visible spectroscopic studies indicate that the title hydrated salt is stable in solution. Density functional theory (DFT) studies reveal that the geometric parameters of [Co^(II)Cl(TMC)]Cl·2H_2O are sensitive to the cobalt spin state and correctly predict a change in spin state upon a minor perturbation to the ligand environment.

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Takase, Michael K.0000-0001-8365-3645
Additional Information:© 2017 International Union of Crystallography. Received 29 April 2017; accepted 13 July 2017; online 20 July 2017. We thank Professor Adam Johnson (Harvey Mudd College) for helpful discussions. This work was funded by the Department of Chemistry at Harvey Mudd College, the Hixon Center for Sustainable Environmental Design at Harvey Mudd College through its Rasmussen Summer Research Fund (to CY), the Rose Hills Foundation (to IL), and the Harris Family Research Fellowship in Chemistry honoring Professor Emeritus Philip C. Myhre (to RG). This work used the Extreme Science and Engineering Discovery Environment (XSEDE), which is supported by National Science Foundation grant No. ACI-1548562.
Funding AgencyGrant Number
Harvey Mudd CollegeUNSPECIFIED
Rose Hills FoundationUNSPECIFIED
Harris Family Research FellowshipUNSPECIFIED
Subject Keywords:divalent cobalt; tetra­aza­macrocycle; UV–visible spectroscopy; density functional theory; crystal structure; computational chemistry
Issue or Number:8
Record Number:CaltechAUTHORS:20170721-105932439
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Official Citation:Van Heuvelen, K. M., Lee, I., Arriola, K., Griffin, R., Ye, C. & Takase, M. K. (2017). Acta Cryst. C73, 620-624.
Usage Policy:No commercial reproduction, distribution, display or performance rights in this work are provided.
ID Code:79269
Deposited By: Tony Diaz
Deposited On:21 Jul 2017 18:18
Last Modified:15 Nov 2021 17:46

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