TY - JOUR
T1 - Synthesis and properties of new Mo(II) complexes with N-heterocyclic and ferrocenyl ligands
AU - Quintal, Susana
AU - Fedi, Serena
AU - Barbetti, Jacopo
AU - Pinto, Patrícia
AU - Félix, Vitor
AU - Drew, Michael G.B.
AU - Zanello, Piero
AU - Calhorda, Maria José
N1 - Funding Information:
S. Quintal thanks FCT for a post-doc fellowship (SFRH/BPD/11463/2002 and SFRD/BPD/27454/2006). The University of Reading and EPSRC are thanked for funds for the Image Plate and CCD diffractometers. P.Z. is indebted to Dr. Serena Losi for her helpful collaboration in electrochemical measurements. CIRCMSB is acknowledged for the support. MJC acknowledges FCT, POCI and FEDER (project PTDC/QUI/58925/2004) for financial support.
PY - 2011/5/15
Y1 - 2011/5/15
N2 - 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.
AB - 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.
KW - DFT calculations
KW - Electrochemistry
KW - Ferrocenyl ligands
KW - Mo(II) complexes
KW - Spectroelectrochemistry
KW - X-ray crystal structures
UR - http://www.scopus.com/inward/record.url?scp=79955055687&partnerID=8YFLogxK
U2 - 10.1016/j.jorganchem.2010.11.024
DO - 10.1016/j.jorganchem.2010.11.024
M3 - Article
SN - 0022-328X
VL - 696
SP - 2142
EP - 2152
JO - Journal of Organometallic Chemistry
JF - Journal of Organometallic Chemistry
IS - 10
ER -