O-atom-transfer oxidation of [molybdenum(IV) oxo{3,6-(acylamino)2- 1,2-benzenedithiolato}2]2- promoted by intramolecular NH...S hydrogen bonds.
Novel molybdenum dithiolene compounds having neighboring amide groups as models for molybdoenzymes, (NEt(4))(2)[Mo(IV)O{1,2-S(2)-3,6-(RCONH)(2)C(6)H(2)}(2)] (R = CH(3), CF(3), t-Bu, Ph(3)C), were designed and synthesized. The contributions of the NH...S hydrogen bond to the electrochemical properties of the metal ion and the reactivity of the O-atom-transfer reaction were investigated by a comparison with [Mo(IV)O(1,2-S(2)C(6)H(4))(2)](2)(-). The MoOS(4) core of [Mo(IV)O{1,2-S(2)-3,6-(CH(3)CONH)(2)C(6)H(2)}(2)](2)(-) shows no significant geometrical difference from that of [Mo(IV)O(1,2-S(2)C(6)H(4))(2)](2)(-) in the crystal. The hydrogen bonds positively shifted the Mo(IV/V) redox potential and accelerated the reduction of Me(3)NO.
Baba
Koji
K
Chemical Analysis Research Center, National Institute for Agro-Environmental Sciences, Tsukuba, Ibaraki 305-8604, Japan.
Okamura
Taka-aki
TA
Suzuki
Chie
C
Yamamoto
Hitoshi
H
Yamamoto
Tetsuo
T
Ohama
Mitsuo
M
Ueyama
Norikazu
N
D018360:Crystallography, X-Ray; D004563:Electrochemistry; D006860:Hydrogen Bonding; D008744:Methylamines / Q000737:chemistry; D008958:Models, Molecular; D015394:Molecular Structure; D008982:Molybdenum / Q000737:chemistry*; D009942:Organometallic Compounds / Q000138:chemical synthesis* / Q000737:chemistry*; D010084:Oxidation-Reduction; D010100:Oxygen / Q000737:chemistry*; D012680:Sensitivity and Specificity; D013055:Spectrophotometry, Infrared / Q000379:methods; D013059:Spectrum Analysis, Raman / Q000379:methods; D013438:Sulfhydryl Compounds / Q000737:chemistry*
D008744:Methylamines; D009942:Organometallic Compounds; D013438:Sulfhydryl Compounds; D008982:Molybdenum; C005855:trimethyloxamine; D010100:Oxygen