Cadmium-113 NMR studies on homoleptic complexes containing thioether ligands: The crystal structures of [Cd([12]aneS 4) 2] (ClO 4) 2, [Cd([18]aneS 4N 2)](PF 6) 2 and [Cd([9]aneS 3) 2](PF 6) 2

Monte Helm, Lensey L. Hill, John P. Lee, Donald G. Van Derveer, Gregory J. Grant

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Abstract

We report the measurement of 113Cd NMR chemical shift data for homoleptic thioether and related aza and mixed aza/thiacrown complexes. In a series of Cd(ii) complexes containing trithioether to hexathioether ligands, we observe solution 113Cd NMR chemical shifts in the range of 225 to 731 ppm. Upfield chemical shifts in these NMR spectra are seen whenever: (a) the number of thioether sulfur donors in the complex is decreased, (b) a thioether sulfur donor is replaced by a secondary nitrogen donor, or (c) the size of the macrocycle ring increases without a change in the nature or number of the donor atoms. Changes in the identity of non-coordinating anions such as perchlorate or hexafluorophosphate have little effect upon the 113Cd NMR chemical shift in solution. We report the X-ray structure of the complex [Cd([12]aneS 4) 2](ClO 4) 2 ([12]aneS 4 = 1,4,7,10-tetrathiacyclododecane) (1) which shows the first example of octakis(thioether) coordination of a metal ion, forming an unusual eight-coordinate square antiprismatic structure. We report the X-ray structure of the complex [Cd([9]aneS 3) 2](PF 6) 2 ([9]aneS 3 = 1,4,7-trithiacyclononane) (3a) which shows hexakis(thioether) coordination to form a distorted octahedral structure. We have also prepared and characterized the Cd(ii) complex of a mixed azathiacrown, [Cd([18]aneS 4N 2)](PF 6) 2 ([18]aneS 4N 2 = 1,4,10,13-tetrathia-7,16- diazacyclooctadecane) (6). Its X-ray structure shows a distorted octahedral S 4N 2 environment around the Cd(ii) with the ligand coordinated in the rac fashion. We observe a solvent- and temperature-dependent 14N- 1H coupling in the 1H NMR spectrum of the complex which is not present in analogous complexes with this ligand.

Original languageEnglish
Pages (from-to)3534-3543
Number of pages10
JournalDalton Transactions
Issue number29
DOIs
Publication statusPublished - 2006

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Sulfides
Cadmium
Chemical shift
Crystal structure
Nuclear magnetic resonance
Ligands
Sulfur
X rays
Anions
Metal ions
Nitrogen
Atoms
Temperature

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  • Chemistry(all)

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Cadmium-113 NMR studies on homoleptic complexes containing thioether ligands : The crystal structures of [Cd([12]aneS 4) 2] (ClO 4) 2, [Cd([18]aneS 4N 2)](PF 6) 2 and [Cd([9]aneS 3) 2](PF 6) 2. / Helm, Monte; Hill, Lensey L.; Lee, John P.; Van Derveer, Donald G.; Grant, Gregory J.

In: Dalton Transactions, No. 29, 2006, p. 3534-3543.

Research output: Contribution to journalArticle

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title = "Cadmium-113 NMR studies on homoleptic complexes containing thioether ligands: The crystal structures of [Cd([12]aneS 4) 2] (ClO 4) 2, [Cd([18]aneS 4N 2)](PF 6) 2 and [Cd([9]aneS 3) 2](PF 6) 2",
abstract = "We report the measurement of 113Cd NMR chemical shift data for homoleptic thioether and related aza and mixed aza/thiacrown complexes. In a series of Cd(ii) complexes containing trithioether to hexathioether ligands, we observe solution 113Cd NMR chemical shifts in the range of 225 to 731 ppm. Upfield chemical shifts in these NMR spectra are seen whenever: (a) the number of thioether sulfur donors in the complex is decreased, (b) a thioether sulfur donor is replaced by a secondary nitrogen donor, or (c) the size of the macrocycle ring increases without a change in the nature or number of the donor atoms. Changes in the identity of non-coordinating anions such as perchlorate or hexafluorophosphate have little effect upon the 113Cd NMR chemical shift in solution. We report the X-ray structure of the complex [Cd([12]aneS 4) 2](ClO 4) 2 ([12]aneS 4 = 1,4,7,10-tetrathiacyclododecane) (1) which shows the first example of octakis(thioether) coordination of a metal ion, forming an unusual eight-coordinate square antiprismatic structure. We report the X-ray structure of the complex [Cd([9]aneS 3) 2](PF 6) 2 ([9]aneS 3 = 1,4,7-trithiacyclononane) (3a) which shows hexakis(thioether) coordination to form a distorted octahedral structure. We have also prepared and characterized the Cd(ii) complex of a mixed azathiacrown, [Cd([18]aneS 4N 2)](PF 6) 2 ([18]aneS 4N 2 = 1,4,10,13-tetrathia-7,16- diazacyclooctadecane) (6). Its X-ray structure shows a distorted octahedral S 4N 2 environment around the Cd(ii) with the ligand coordinated in the rac fashion. We observe a solvent- and temperature-dependent 14N- 1H coupling in the 1H NMR spectrum of the complex which is not present in analogous complexes with this ligand.",
author = "Monte Helm and Hill, {Lensey L.} and Lee, {John P.} and {Van Derveer}, {Donald G.} and Grant, {Gregory J.}",
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T2 - The crystal structures of [Cd([12]aneS 4) 2] (ClO 4) 2, [Cd([18]aneS 4N 2)](PF 6) 2 and [Cd([9]aneS 3) 2](PF 6) 2

AU - Helm, Monte

AU - Hill, Lensey L.

AU - Lee, John P.

AU - Van Derveer, Donald G.

AU - Grant, Gregory J.

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N2 - We report the measurement of 113Cd NMR chemical shift data for homoleptic thioether and related aza and mixed aza/thiacrown complexes. In a series of Cd(ii) complexes containing trithioether to hexathioether ligands, we observe solution 113Cd NMR chemical shifts in the range of 225 to 731 ppm. Upfield chemical shifts in these NMR spectra are seen whenever: (a) the number of thioether sulfur donors in the complex is decreased, (b) a thioether sulfur donor is replaced by a secondary nitrogen donor, or (c) the size of the macrocycle ring increases without a change in the nature or number of the donor atoms. Changes in the identity of non-coordinating anions such as perchlorate or hexafluorophosphate have little effect upon the 113Cd NMR chemical shift in solution. We report the X-ray structure of the complex [Cd([12]aneS 4) 2](ClO 4) 2 ([12]aneS 4 = 1,4,7,10-tetrathiacyclododecane) (1) which shows the first example of octakis(thioether) coordination of a metal ion, forming an unusual eight-coordinate square antiprismatic structure. We report the X-ray structure of the complex [Cd([9]aneS 3) 2](PF 6) 2 ([9]aneS 3 = 1,4,7-trithiacyclononane) (3a) which shows hexakis(thioether) coordination to form a distorted octahedral structure. We have also prepared and characterized the Cd(ii) complex of a mixed azathiacrown, [Cd([18]aneS 4N 2)](PF 6) 2 ([18]aneS 4N 2 = 1,4,10,13-tetrathia-7,16- diazacyclooctadecane) (6). Its X-ray structure shows a distorted octahedral S 4N 2 environment around the Cd(ii) with the ligand coordinated in the rac fashion. We observe a solvent- and temperature-dependent 14N- 1H coupling in the 1H NMR spectrum of the complex which is not present in analogous complexes with this ligand.

AB - We report the measurement of 113Cd NMR chemical shift data for homoleptic thioether and related aza and mixed aza/thiacrown complexes. In a series of Cd(ii) complexes containing trithioether to hexathioether ligands, we observe solution 113Cd NMR chemical shifts in the range of 225 to 731 ppm. Upfield chemical shifts in these NMR spectra are seen whenever: (a) the number of thioether sulfur donors in the complex is decreased, (b) a thioether sulfur donor is replaced by a secondary nitrogen donor, or (c) the size of the macrocycle ring increases without a change in the nature or number of the donor atoms. Changes in the identity of non-coordinating anions such as perchlorate or hexafluorophosphate have little effect upon the 113Cd NMR chemical shift in solution. We report the X-ray structure of the complex [Cd([12]aneS 4) 2](ClO 4) 2 ([12]aneS 4 = 1,4,7,10-tetrathiacyclododecane) (1) which shows the first example of octakis(thioether) coordination of a metal ion, forming an unusual eight-coordinate square antiprismatic structure. We report the X-ray structure of the complex [Cd([9]aneS 3) 2](PF 6) 2 ([9]aneS 3 = 1,4,7-trithiacyclononane) (3a) which shows hexakis(thioether) coordination to form a distorted octahedral structure. We have also prepared and characterized the Cd(ii) complex of a mixed azathiacrown, [Cd([18]aneS 4N 2)](PF 6) 2 ([18]aneS 4N 2 = 1,4,10,13-tetrathia-7,16- diazacyclooctadecane) (6). Its X-ray structure shows a distorted octahedral S 4N 2 environment around the Cd(ii) with the ligand coordinated in the rac fashion. We observe a solvent- and temperature-dependent 14N- 1H coupling in the 1H NMR spectrum of the complex which is not present in analogous complexes with this ligand.

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