Cationic acetyl complexes of iron(II) and ruthenium(II) bearing neutral N,O ligands

Synthesis, characterization, and interionic solution structure by NOESY NMR spectroscopy

Gianfranco Bellachioma, Giuseppe Cardaci, Volker Gramlich, Alceo Macchioni, Massimiliano Valentini, Cristiano Zuccaccia

Research output: Contribution to journalArticle

34 Citations (Scopus)

Abstract

The reactions of complexes trans, cis-M(PMe3)2(CO)2(Me)I (M = Fe (1a), Ru (1b)) with N,O ligands [2-acetylpyridine (2-apy), 2-benzoylpyridine (2-bzpy), and 2,2′-dipyridyl ketone (2,2′-dpk)] in the presence of NaBPh4 afford a mixture of the two possible stereoisomers trans-[M(PMe3)2(CO)(COMe)(N, O)]BPh4 having the N arm cis (A) or trans (B) to the acetyl group. The stereochemistry of the complexes was determined by 1H NOESY NMR spectra. For all the iron complexes the major stereoisomer is B, while for ruthenium complexes it is A. When A/B mixtures are left in methylene chloride, the concentration of A increases, indicating that A and B are the thermodynamic and kinetic reaction products, respectively. Furthermore, the more basic the N,O ligands, the more B stereoisomer that forms. The solid-state structure of 4b was obtained using single-crystal X-ray diffraction. For all the complexes, the ion-pair structures and the localization of the counterion in solution with respect to the organometallic moiety were investigated by the detection of interionic contacts in the 1H NOESY NMR spectra. Specific interactions were observed that indicate that the counterion is localized in solution in front of the face determined by PMe3 and the two arms of the N,O ligands.

Original languageEnglish
Pages (from-to)5025-5030
Number of pages6
JournalOrganometallics
Volume17
Issue number23
Publication statusPublished - 1998

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Bearings (structural)
Stereoisomerism
Ruthenium
Nuclear magnetic resonance spectroscopy
ruthenium
Iron
Carbon Monoxide
Ligands
iron
nuclear magnetic resonance
ligands
synthesis
Nuclear magnetic resonance
spectroscopy
Stereochemistry
Methylene Chloride
stereochemistry
Organometallics
Ketones
Reaction products

ASJC Scopus subject areas

  • Inorganic Chemistry
  • Organic Chemistry

Cite this

Cationic acetyl complexes of iron(II) and ruthenium(II) bearing neutral N,O ligands : Synthesis, characterization, and interionic solution structure by NOESY NMR spectroscopy. / Bellachioma, Gianfranco; Cardaci, Giuseppe; Gramlich, Volker; Macchioni, Alceo; Valentini, Massimiliano; Zuccaccia, Cristiano.

In: Organometallics, Vol. 17, No. 23, 1998, p. 5025-5030.

Research output: Contribution to journalArticle

Bellachioma, Gianfranco ; Cardaci, Giuseppe ; Gramlich, Volker ; Macchioni, Alceo ; Valentini, Massimiliano ; Zuccaccia, Cristiano. / Cationic acetyl complexes of iron(II) and ruthenium(II) bearing neutral N,O ligands : Synthesis, characterization, and interionic solution structure by NOESY NMR spectroscopy. In: Organometallics. 1998 ; Vol. 17, No. 23. pp. 5025-5030.
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N2 - The reactions of complexes trans, cis-M(PMe3)2(CO)2(Me)I (M = Fe (1a), Ru (1b)) with N,O ligands [2-acetylpyridine (2-apy), 2-benzoylpyridine (2-bzpy), and 2,2′-dipyridyl ketone (2,2′-dpk)] in the presence of NaBPh4 afford a mixture of the two possible stereoisomers trans-[M(PMe3)2(CO)(COMe)(N, O)]BPh4 having the N arm cis (A) or trans (B) to the acetyl group. The stereochemistry of the complexes was determined by 1H NOESY NMR spectra. For all the iron complexes the major stereoisomer is B, while for ruthenium complexes it is A. When A/B mixtures are left in methylene chloride, the concentration of A increases, indicating that A and B are the thermodynamic and kinetic reaction products, respectively. Furthermore, the more basic the N,O ligands, the more B stereoisomer that forms. The solid-state structure of 4b was obtained using single-crystal X-ray diffraction. For all the complexes, the ion-pair structures and the localization of the counterion in solution with respect to the organometallic moiety were investigated by the detection of interionic contacts in the 1H NOESY NMR spectra. Specific interactions were observed that indicate that the counterion is localized in solution in front of the face determined by PMe3 and the two arms of the N,O ligands.

AB - The reactions of complexes trans, cis-M(PMe3)2(CO)2(Me)I (M = Fe (1a), Ru (1b)) with N,O ligands [2-acetylpyridine (2-apy), 2-benzoylpyridine (2-bzpy), and 2,2′-dipyridyl ketone (2,2′-dpk)] in the presence of NaBPh4 afford a mixture of the two possible stereoisomers trans-[M(PMe3)2(CO)(COMe)(N, O)]BPh4 having the N arm cis (A) or trans (B) to the acetyl group. The stereochemistry of the complexes was determined by 1H NOESY NMR spectra. For all the iron complexes the major stereoisomer is B, while for ruthenium complexes it is A. When A/B mixtures are left in methylene chloride, the concentration of A increases, indicating that A and B are the thermodynamic and kinetic reaction products, respectively. Furthermore, the more basic the N,O ligands, the more B stereoisomer that forms. The solid-state structure of 4b was obtained using single-crystal X-ray diffraction. For all the complexes, the ion-pair structures and the localization of the counterion in solution with respect to the organometallic moiety were investigated by the detection of interionic contacts in the 1H NOESY NMR spectra. Specific interactions were observed that indicate that the counterion is localized in solution in front of the face determined by PMe3 and the two arms of the N,O ligands.

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