The first designed syntheses of bis-dimetal molecules in which the bridges are diamidate ligands.
The first deliberate syntheses of molecules in which pairs of quadruply bonded Mo2 units are bridged by N,N'-diarylterephthaloyldiamidate (aryl = Ph, m-CF3Ph) ligands are described. The addition of neutral N,N'-diarylterephthaloyldiamide to 2 equiv of [Mo2(DAniF)3(MeCN)2]+ (DAniF = N,N'-di-p-anisylformamidinate) followed by the introduction of excess H3CO- in MeCN results in the formation of (DAniF)3Mo2[(C6H5)NC(O)C6H4(O)CN(C6H5)]Mo2(DAniF)3 (1) and (DAniF)3Mo2[[(m-CF3)C6H5]NC(O)C6H4(O)CN[(m-CF3)C6H5]]Mo2(DAniF)3 (2). The DeltaE1/2 for the oxidation of each Mo2 unit is greater for these terephthaloyldiamidate-bridged molecules (approximately 100 mV) than for the analogous terephthalate-bridged compound (approximately 60 mV). Variation in the nature of the substituents on the diamidate nitrogen atoms offers a means to fine-tune the oxidation potentials of the Mo2 units.
Cotton
F Albert
FA
Department of Chemistry and Laboratory for Molecular Structure and Bonding, P.O. Box 30012, Texas A&M University, College Station, Texas 77842-3012, USA. cotton@tamu.edu
Daniels
Lee M
LM
Donahue
James P
JP
Liu
Chun Y
CY
Murillo
Carlos A
CA
D001952:Bridged-Ring Compounds / Q000138:chemical synthesis* / Q000737:chemistry; D002384:Catalysis; D018360:Crystallography, X-Ray; D003958:Diamide / Q000737:chemistry*; D004563:Electrochemistry / Q000379:methods; D008024:Ligands; D008968:Molecular Conformation; D015394:Molecular Structure; D008982:Molybdenum / Q000737:chemistry*; D009942:Organometallic Compounds / Q000138:chemical synthesis* / Q000737:chemistry; D012211:Rhenium / Q000737:chemistry
C453544:(DAniF)3Mo2(((m-CF3)C6H5)NC(O)C6H4(O)CN((m-CF3)C6H5))Mo2(DAniF)3; C453545:(DAniF)3Mo2((C6H5)NC(O)C6H4(O)CN(C6H5))Mo2(DAniF)3; D001952:Bridged-Ring Compounds; D008024:Ligands; D009942:Organometallic Compounds; D003958:Diamide; D012211:Rhenium; D008982:Molybdenum