Synthesis and properties of new Mo(II) complexes with N-heterocyclic and ferrocenyl ligands

Susana Quintal, Serena Fedi, Jacopo Barbetti, Patrícia Pinto, Vitor Félix, Michael G.B. Drew, Piero Zanello, Maria José Calhorda

Research output: Contribution to journalArticlepeer-review

12 Citations (Scopus)

Abstract

New Mo(II) complexes with 2,2′-dipyridylamine (L1), [Mo(CH 3CN)(η3-C3H5)(CO) 2(L1)]OTf (C1a) and [{MoBr(η3-C3H 5)(CO)2(L1)}2(4,4′-bipy)](PF 6)2 (C1b), with {[bis(2-pyridyl)amino]carbonyl}ferrocene (L2), [MoBr(η3-C3H5)(CO)2(L2)] (C2), and with the new ligand N,N-bis(ferrocenecarbonyl)-2-aminopyridine (L3), [MoBr(η3-C3H5)(CO)2(L3)] (C3), were prepared and characterized by FTIR and 1H and 13C NMR spectroscopy. C1a, C1b, L3, and C2 were also structurally characterized by single crystal X-ray diffraction. The Mo(II) coordination sphere in all complexes features the facial arrangement of allyl and carbonyl ligands, with the axial isomer present in C1a and C2, and the equatorial in the binuclear C1b. In both C1a and C1b complexes, the L1 ligand is bonded to Mo(II) through the nitrogen atoms and the NH group is involved in hydrogen bonds. The X-ray single crystal structure of C2 shows that L2 is coordinated in a κ2-N, N-bidentate chelating fashion. Complex C3 was characterized as [MoBr(η3-C3H5)(CO)2(L3)] with L3 acting as a κ2-N,O-bidentate ligand, based on the spectroscopic data, complemented by DFT calculations. The electrochemical behavior of the monoferrocenyl and diferrocenyl ligands L2 and L3 has been studied together with that of their Mo(II) complexes C2 and C3. As much as possible, the nature of the different redox changes has been confirmed by spectrophotometric measurements. The nature of the frontier orbitals, namely the localization of the HOMO in Mo for both in C2 and C3, was determined by DFT studies.

Original languageEnglish
Pages (from-to)2142-2152
Number of pages11
JournalJournal of Organometallic Chemistry
Volume696
Issue number10
DOIs
Publication statusPublished - 15 May 2011

Keywords

  • DFT calculations
  • Electrochemistry
  • Ferrocenyl ligands
  • Mo(II) complexes
  • Spectroelectrochemistry
  • X-ray crystal structures

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