Na2[(mu-N,N'-C10H12N2O8)(mu-O)(mu-S)-Mo2O2].2H2O

Area of Science:

• Inorganic Chemistry
• Coordination Chemistry
• Molybdenum Chemistry

Background:

• Bridging-oxo complexes of dimolybdenum(V) are well-established.
• Analogs with sulfide bridges are known, but mixed oxo-sulfido complexes offer unique properties.

Purpose of the Study:

• To synthesize and characterize a novel unsymmetrical dimolybdenum(V) complex with both oxo and sulfido bridges.
• To investigate the structural and bonding characteristics of the mixed-bridged complex.

Main Methods:

• Reduction of a dimolybdenum(V) precursor, [(MoO3)2(mu-edta)]4-, with dithionite.
• In situ generation of sulfide to replace an oxide bridge.
• Infrared (IR) and Nuclear Magnetic Resonance (NMR) spectroscopy for analysis.
• X-ray crystallography for molecular structure determination.

Main Results:

• Successful synthesis of disodium mu-(ethylenediaminetetraacetato)-mu-oxo-mu-sulfido-bis[oxomolybdenum(V)] dihydrate, Na2-[Mo2O3S(C10H12N2O8)].2H2O.
• IR and NMR data indicate an unsymmetrical complex structure.
• X-ray crystallography revealed distorted octahedral coordination at Mo centers.
• Average Mo-S bond distance of 2.320 Å and Mo-O bond distance of 1.938 Å.
• Mo...Mo contact distance of 2.666 Å, intermediate between di-mu-oxo and di-mu-sulfido complexes.

Conclusions:

• The study successfully synthesized and characterized a novel unsymmetrical mixed oxo-sulfido dimolybdenum(V) complex.
• The structural data provides insights into the bonding and electronic properties of such complexes.
• The intermediate Mo-Mo distance suggests a unique electronic interaction in the mixed-bridged system.