Quadridentate bridging EO(4)(2-) (E = S, Mo, W) ligands and their role as electronic bridges.
Three compounds containing two quadruply bonded Mo(2)(DAniF)(3) (DAniF = N,N'-di-p-anisylformamidinate) units linked by tetrahedral EO(4)(2-) anions (E = S, Mo, W) have been prepared and characterized by crystallography and NMR. The linkers in these [Mo(2)(DAniF)(3)](2)(mu-EO(4)) compounds hold the Mo(2) units in an approximately perpendicular orientation and mediate strong electrochemical communication between them. Each of the three compounds shows two quasireversible (mu-SO(4)) or fully reversible (mu-MoO(4), mu-WO(4)) features in its cyclic voltammogram corresponding to successive oxidation of each of its Mo(2) units. The DeltaE(1/2) values are the largest thus far measured for Mo(2)-X-Mo(2) bridged complexes and may be sufficiently large to permit isolation of the singly oxidized species.
Cotton
F A
FA
Laboratory for Molecular Structure and Bonding, Department of Chemistry, Texas A&M University, PO Box 30012, College Station, Texas 77842-3012, USA. cotton@tamu.edu
Donahue
J P
JP
Murillo
C A
CA
D018360:Crystallography, X-Ray; D004563:Electrochemistry; D007202:Indicators and Reagents; D008024:Ligands; D009682:Magnetic Resonance Spectroscopy; D008982:Molybdenum; D009942:Organometallic Compounds / Q000737:chemistry*; D010100:Oxygen / Q000737:chemistry*; D013455:Sulfur; D014414:Tungsten
D007202:Indicators and Reagents; D008024:Ligands; C430764:Mo(2)(DAniF)(3); D009942:Organometallic Compounds; D013455:Sulfur; D008982:Molybdenum; D010100:Oxygen; D014414:Tungsten