TY - JOUR
T1 - Aqueous reduction of [Cp*2W2O5]
T2 - Characterization of the triangular clusters [Cp*3W 3O4(OH)2]2+ and [Cp* 3W3O6]+ - Comparison with molybdenum
AU - Dinoi, Chiara
AU - Sözen, Pelin
AU - Taban, Gülnur
AU - Demir, Deniz
AU - Demirhan, Funda
AU - Prikhodchenko, Petr
AU - Gun, Jenny
AU - Lev, Ovadia
AU - Daran, Jean Claude
AU - Poli, Rinaldo
PY - 2007
Y1 - 2007
N2 - Zinc reduction of Cp*2W2O5 in an acidified water-methanol medium affords the green 3-electron trinuclear cluster [Cp*3W3O4(OH)2]2+, isolated and crystallographically characterized as the triflate salt, 1. Upon exposure to air, this complex is oxidized to a related 2-electron cluster, [Cp*3W3O6]+, which was crystallized and characterized in three different salts, 2-4. The 3-electron cluster exhibits a near-tetragonal frozen-glass EPR spectrum, and it shows evidence of coupling of the unpaired electron to only one of the three W atoms. The two-electron cluster is diamagnetic. An electrospray ionization MS n study revealed a stepwise expulsion of neutral [Cp*WO 2] units as the main fragmentation process. DFT calculations unveiled the intimate details of the electronic structures of these complexes and fully rationalized the structural and spectroscopic properties.
AB - Zinc reduction of Cp*2W2O5 in an acidified water-methanol medium affords the green 3-electron trinuclear cluster [Cp*3W3O4(OH)2]2+, isolated and crystallographically characterized as the triflate salt, 1. Upon exposure to air, this complex is oxidized to a related 2-electron cluster, [Cp*3W3O6]+, which was crystallized and characterized in three different salts, 2-4. The 3-electron cluster exhibits a near-tetragonal frozen-glass EPR spectrum, and it shows evidence of coupling of the unpaired electron to only one of the three W atoms. The two-electron cluster is diamagnetic. An electrospray ionization MS n study revealed a stepwise expulsion of neutral [Cp*WO 2] units as the main fragmentation process. DFT calculations unveiled the intimate details of the electronic structures of these complexes and fully rationalized the structural and spectroscopic properties.
KW - Density functional calculations
KW - Metal clusters
KW - O ligands
KW - Tungsten
UR - http://www.scopus.com/inward/record.url?scp=34948820124&partnerID=8YFLogxK
U2 - 10.1002/ejic.200700419
DO - 10.1002/ejic.200700419
M3 - ???researchoutput.researchoutputtypes.contributiontojournal.article???
AN - SCOPUS:34948820124
SN - 1434-1948
SP - 4306
EP - 4316
JO - European Journal of Inorganic Chemistry
JF - European Journal of Inorganic Chemistry
IS - 27
ER -