L. Stelzig et al., MOLYBDENUM COMPLEXES WITH TRIDENTATE NS2 LIGANDS - SYNTHESIS, CRYSTAL-STRUCTURES AND SPECTROSCOPIC PROPERTIES, Journal of the Chemical Society. Dalton transactions, (17), 1998, pp. 2921-2926
Reaction of the new tridentate NS, ligands 2-HSC6H4C(Me)=NNHC(S)SCH2Ph
(H2L1), 2-HSC6H4C(Me)=NNHC(S)NHCPh3 (H2L2), 2-HSC6H4CH=NNHC(S)NHCPh3
(H2L3) and 1-Ph-3-Me-5-HS-C3N2-CH=NNC(SH)-NHCPh3 (H2L4) with dioxomoly
bdenum(VI) precursors yielded mononuclear molybdenum(VI) complexes [Mo
O2(L-1)(pic)] 1 (pic = 4-methylpyridine), [MoO2L2(MeOH)]. 2.25 MeOH 2
and the dinuclear molybdenum(v) complexes [Mo2O3L23]. 3CH(2)Cl(2) 3 an
d [Mo2O3L24] 4. The molecular structures of 1-3 were determined by sin
gle-crystal X-ray analysis. Complexes 1 and 2 each consist of a centra
l cis-MoO2 unit with a mer co-ordinating tridentate dianionic ligand a
nd one neutral donor molecule completing the octahedral environment of
molybdenum(VI). Complex 3 exhibits an anti-Mo2O3 group co-ordinated b
y two mer chelating ligands. The symmetry-related molybdenum(v) centre
s are in a square pyramidal environment. Infrared, NMR and MS studies
evidenced a comparable structure for 4. The reduction of the dioxomoly
bdenum(VI) compounds 1 and 2, achieved by addition of phosphines like
PPh3, also leads to dinuclear mu-oxo-bridged complexes. The reverse ox
idations of the oxomolybdenum(v) complexes are restricted by the natur
e of the ligand and the oxidizing agents.