Synthesis and characterization of molybdenum oxo complexes of two tripodal ligands: reactivity studies of a functional model for molybdenum oxotransferases.
Reaction of the tetradentate ligand N-(2-hydroxybenzyl)-N,N-bis(2-pyridylmethyl)amine (L-OH) with MoO2Cl2 in methanol in the presence of NaOMe and PF6- results in the formation of [MoO2(L-O)]PF6. Similarly, the reaction of N-(2-mercaptobenzyl)-N,N-bis(2-pyridylmethyl)amine (L-SH) with MoO2(acac)2 leads to the formation of [MoO2(L-S)]+. The dioxo-molybdenum complex [MoO2(L-O)]+ reacts with phosphines in methanol to afford phosphine oxides and an air-sensitive molybdenum complex, tentatively identified as [Mo(IV)O(L-O)(OCH3)]. The latter complex is capable of reducing biological oxygen donors such as DMSO or nitrate, thereby mimicking the activity of DMSO reductase and nitrate reductase. Reaction of [MoO2(L-O)]PF6 with PPh3 in other solvents than methanol leads to the formation of the Mo(V) dimer [(L-O)OMo(micro-O)MoO(L-O)](PF6)2. The crystal structures of [MoO2(L-O)]PF6 and the micro-oxo bridged dimer are presented.
Thapper
Anders
A
Inorganic Chemistry, Center for Chemistry and Chemical Engineering, Lund University, Box 124, SE-221 00, Lund, Sweden.
Behrens
Axel
A
Fryxelius
Jacob
J
Johansson
Maria H
MH
Prestopino
Fabio
F
Czaun
Miklós
M
Rehder
Dieter
D
Nordlander
Ebbe
E
D018360:Crystallography, X-Ray; D008024:Ligands; D009682:Magnetic Resonance Spectroscopy; D008958:Models, Molecular; D008968:Molecular Conformation; D008982:Molybdenum / Q000737:chemistry* / Q000378:metabolism*; D010088:Oxidoreductases / Q000737:chemistry* / Q000378:metabolism*; D010100:Oxygen / Q000737:chemistry* / Q000378:metabolism*
D008024:Ligands; D008982:Molybdenum; D010088:Oxidoreductases; C100768:dimethylsulfide - acceptor oxidoreductase; D010100:Oxygen