Synthetic, structural, spectroscopic, and electrochemical studies of mixed sandwich Rh(III) and Ir(III) complexes involving Cp* and tridentate macrocycles

Gregory J. Grant, John P. Lee, Monte Helm, Donald G. VanDerveer, William T. Pennington, Jeffrey L. Harris, Larry F. Mehne, David W. Klinger

Research output: Contribution to journalArticle

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Abstract

The syntheses, structures, spectroscopy, and electrochemistry for six Ir(III) and Rh(III) mixed sandwich mononuclear complexes involving tridentate macrocycles and pentamethylcyclopentadienide (Cp*) are reported. The complexes are readily prepared by direct ligand substitution reactions from the dichloro bridged binuclear complexes, [{M(Cp*)(Cl)2} 2]. All complexes have the general formula [M(L)(Cp*)]X 2 (M = Ir(III) or Rh(III), L = macrocycle, X = PF6 - or Cl-) and exhibit a distorted octahedral structure involving three donor atoms from the macrocycle and the facially coordinating carbocyclic Cp* ligand. The complex cations include: [Rh(η 5-Cp*)(9S3)]2+ (1), [Rh(η5-Cp*) (9N3)]2+ (2), [Rh(η5-Cp*)(10S3)]2+ (3), [Ir(η5-Cp*)(9S3)]2+ (4), [Ir(η5-Cp*)(9N3)]2+ (5), and [Ir(η5-Cp*)(10S3)]2+ (6), where 9S3 = 1,4,7-trithiacyclononane, 9N3 = 1,4,7-triazacyclononane, and 10S3 = 1,4,7-trithiacyclodecane. The structures for all six complexes are supported by 1H and 13C{1H} NMR spectroscopy, and five complexes are also characterized by single-crystal X-ray crystallography (complexes 1-5). The 1H NMR splittings between the two sets of methylene protons for both the Rh(III) and Ir(III) 9S3 complexes are much larger (0.4 vs. 0.2 ppm) compared to those in the two 9N3 complexes. Similarly, the 13C{1H} NMR spectra in all four thioether complexes show that the ring carbons in the Cp* ligand are shifted by over 10 ppm down.eld compared to the azacrown complexes. The electrochemistry of the complexes is surprisingly invariable and is dominated by a single irreversible metal-centered reduction near - 1.2 V vs. Fc/Fc+.

Original languageEnglish
Pages (from-to)629-639
Number of pages11
JournalJournal of Organometallic Chemistry
Volume690
Issue number3
DOIs
Publication statusPublished - Jan 28 2005

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Electrochemistry
Ligands
electrochemistry
nuclear magnetic resonance
ligands
Nuclear magnetic resonance
X ray crystallography
X Ray Crystallography
Sulfides
methylene
spectroscopy
Nuclear magnetic resonance spectroscopy
crystallography
Cations
Protons
Spectrum Analysis
Substitution reactions
Magnetic Resonance Spectroscopy
Carbon
Positive ions

Keywords

  • 1,4,7-Trithiacyclononane
  • Iridium complexes
  • Macrocyclic ligands
  • Mixed sandwich complexes
  • Pentamethylcyclopentadienide complexes
  • Rhodium complexes

ASJC Scopus subject areas

  • Chemical Engineering (miscellaneous)
  • Materials Science (miscellaneous)
  • Materials Chemistry
  • Physical and Theoretical Chemistry
  • Organic Chemistry
  • Inorganic Chemistry
  • Biochemistry

Cite this

Synthetic, structural, spectroscopic, and electrochemical studies of mixed sandwich Rh(III) and Ir(III) complexes involving Cp* and tridentate macrocycles. / Grant, Gregory J.; Lee, John P.; Helm, Monte; VanDerveer, Donald G.; Pennington, William T.; Harris, Jeffrey L.; Mehne, Larry F.; Klinger, David W.

In: Journal of Organometallic Chemistry, Vol. 690, No. 3, 28.01.2005, p. 629-639.

Research output: Contribution to journalArticle

Grant, Gregory J. ; Lee, John P. ; Helm, Monte ; VanDerveer, Donald G. ; Pennington, William T. ; Harris, Jeffrey L. ; Mehne, Larry F. ; Klinger, David W. / Synthetic, structural, spectroscopic, and electrochemical studies of mixed sandwich Rh(III) and Ir(III) complexes involving Cp* and tridentate macrocycles. In: Journal of Organometallic Chemistry. 2005 ; Vol. 690, No. 3. pp. 629-639.
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title = "Synthetic, structural, spectroscopic, and electrochemical studies of mixed sandwich Rh(III) and Ir(III) complexes involving Cp* and tridentate macrocycles",
abstract = "The syntheses, structures, spectroscopy, and electrochemistry for six Ir(III) and Rh(III) mixed sandwich mononuclear complexes involving tridentate macrocycles and pentamethylcyclopentadienide (Cp*) are reported. The complexes are readily prepared by direct ligand substitution reactions from the dichloro bridged binuclear complexes, [{M(Cp*)(Cl)2} 2]. All complexes have the general formula [M(L)(Cp*)]X 2 (M = Ir(III) or Rh(III), L = macrocycle, X = PF6 - or Cl-) and exhibit a distorted octahedral structure involving three donor atoms from the macrocycle and the facially coordinating carbocyclic Cp* ligand. The complex cations include: [Rh(η 5-Cp*)(9S3)]2+ (1), [Rh(η5-Cp*) (9N3)]2+ (2), [Rh(η5-Cp*)(10S3)]2+ (3), [Ir(η5-Cp*)(9S3)]2+ (4), [Ir(η5-Cp*)(9N3)]2+ (5), and [Ir(η5-Cp*)(10S3)]2+ (6), where 9S3 = 1,4,7-trithiacyclononane, 9N3 = 1,4,7-triazacyclononane, and 10S3 = 1,4,7-trithiacyclodecane. The structures for all six complexes are supported by 1H and 13C{1H} NMR spectroscopy, and five complexes are also characterized by single-crystal X-ray crystallography (complexes 1-5). The 1H NMR splittings between the two sets of methylene protons for both the Rh(III) and Ir(III) 9S3 complexes are much larger (0.4 vs. 0.2 ppm) compared to those in the two 9N3 complexes. Similarly, the 13C{1H} NMR spectra in all four thioether complexes show that the ring carbons in the Cp* ligand are shifted by over 10 ppm down.eld compared to the azacrown complexes. The electrochemistry of the complexes is surprisingly invariable and is dominated by a single irreversible metal-centered reduction near - 1.2 V vs. Fc/Fc+.",
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TY - JOUR

T1 - Synthetic, structural, spectroscopic, and electrochemical studies of mixed sandwich Rh(III) and Ir(III) complexes involving Cp* and tridentate macrocycles

AU - Grant, Gregory J.

AU - Lee, John P.

AU - Helm, Monte

AU - VanDerveer, Donald G.

AU - Pennington, William T.

AU - Harris, Jeffrey L.

AU - Mehne, Larry F.

AU - Klinger, David W.

PY - 2005/1/28

Y1 - 2005/1/28

N2 - The syntheses, structures, spectroscopy, and electrochemistry for six Ir(III) and Rh(III) mixed sandwich mononuclear complexes involving tridentate macrocycles and pentamethylcyclopentadienide (Cp*) are reported. The complexes are readily prepared by direct ligand substitution reactions from the dichloro bridged binuclear complexes, [{M(Cp*)(Cl)2} 2]. All complexes have the general formula [M(L)(Cp*)]X 2 (M = Ir(III) or Rh(III), L = macrocycle, X = PF6 - or Cl-) and exhibit a distorted octahedral structure involving three donor atoms from the macrocycle and the facially coordinating carbocyclic Cp* ligand. The complex cations include: [Rh(η 5-Cp*)(9S3)]2+ (1), [Rh(η5-Cp*) (9N3)]2+ (2), [Rh(η5-Cp*)(10S3)]2+ (3), [Ir(η5-Cp*)(9S3)]2+ (4), [Ir(η5-Cp*)(9N3)]2+ (5), and [Ir(η5-Cp*)(10S3)]2+ (6), where 9S3 = 1,4,7-trithiacyclononane, 9N3 = 1,4,7-triazacyclononane, and 10S3 = 1,4,7-trithiacyclodecane. The structures for all six complexes are supported by 1H and 13C{1H} NMR spectroscopy, and five complexes are also characterized by single-crystal X-ray crystallography (complexes 1-5). The 1H NMR splittings between the two sets of methylene protons for both the Rh(III) and Ir(III) 9S3 complexes are much larger (0.4 vs. 0.2 ppm) compared to those in the two 9N3 complexes. Similarly, the 13C{1H} NMR spectra in all four thioether complexes show that the ring carbons in the Cp* ligand are shifted by over 10 ppm down.eld compared to the azacrown complexes. The electrochemistry of the complexes is surprisingly invariable and is dominated by a single irreversible metal-centered reduction near - 1.2 V vs. Fc/Fc+.

AB - The syntheses, structures, spectroscopy, and electrochemistry for six Ir(III) and Rh(III) mixed sandwich mononuclear complexes involving tridentate macrocycles and pentamethylcyclopentadienide (Cp*) are reported. The complexes are readily prepared by direct ligand substitution reactions from the dichloro bridged binuclear complexes, [{M(Cp*)(Cl)2} 2]. All complexes have the general formula [M(L)(Cp*)]X 2 (M = Ir(III) or Rh(III), L = macrocycle, X = PF6 - or Cl-) and exhibit a distorted octahedral structure involving three donor atoms from the macrocycle and the facially coordinating carbocyclic Cp* ligand. The complex cations include: [Rh(η 5-Cp*)(9S3)]2+ (1), [Rh(η5-Cp*) (9N3)]2+ (2), [Rh(η5-Cp*)(10S3)]2+ (3), [Ir(η5-Cp*)(9S3)]2+ (4), [Ir(η5-Cp*)(9N3)]2+ (5), and [Ir(η5-Cp*)(10S3)]2+ (6), where 9S3 = 1,4,7-trithiacyclononane, 9N3 = 1,4,7-triazacyclononane, and 10S3 = 1,4,7-trithiacyclodecane. The structures for all six complexes are supported by 1H and 13C{1H} NMR spectroscopy, and five complexes are also characterized by single-crystal X-ray crystallography (complexes 1-5). The 1H NMR splittings between the two sets of methylene protons for both the Rh(III) and Ir(III) 9S3 complexes are much larger (0.4 vs. 0.2 ppm) compared to those in the two 9N3 complexes. Similarly, the 13C{1H} NMR spectra in all four thioether complexes show that the ring carbons in the Cp* ligand are shifted by over 10 ppm down.eld compared to the azacrown complexes. The electrochemistry of the complexes is surprisingly invariable and is dominated by a single irreversible metal-centered reduction near - 1.2 V vs. Fc/Fc+.

KW - 1,4,7-Trithiacyclononane

KW - Iridium complexes

KW - Macrocyclic ligands

KW - Mixed sandwich complexes

KW - Pentamethylcyclopentadienide complexes

KW - Rhodium complexes

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U2 - 10.1016/j.jorganchem.2004.10.010

DO - 10.1016/j.jorganchem.2004.10.010

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VL - 690

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EP - 639

JO - Journal of Organometallic Chemistry

JF - Journal of Organometallic Chemistry

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