Dramatically accelerated selective oxygen-atom transfer by a nonheme iron(IV)-oxo complex: tuning of the first and second coordination spheres.
The new ligand N3Py(amide)SR and its Fe(II) complex [Fe(II)(N3Py(amide)SR)](BF4)2 (1) are described. Reaction of 1 with PhIO at -40 °C gives metastable [Fe(IV)(O)(N3Py(amide)SR)](2+) (2), containing a sulfide ligand and a single amide H-bond donor in proximity to the terminal oxo group. Direct evidence for H-bonding is seen in a structural analogue, [Fe(II)(Cl)(N3Py(amide)SR)](BF4)2 (3). Complex 2 exhibits rapid O-atom transfer (OAT) toward external sulfide substrates, but no intramolecular OAT. However, direct S-oxygenation does occur in the reaction of 1 with mCPBA, yielding sulfoxide-ligated [Fe(II)(N3Py(amide)S(O)R)](BF4)2 (4). Catalytic OAT with 1 was also observed.
Department of Chemistry, The Johns Hopkins University , 3400 North Charles Street, Baltimore, Maryland 21218, United States.
Leland R
LR
Widger
Casey G
CG
Davies
Tzuhsiung
T
Yang
Maxime A
MA
Siegler
Oliver
O
Troeppner
Guy N L
GN
Jameson
Ivana
I
Ivanović-Burmazović
David P
DP
Goldberg
D006860:Hydrogen Bonding; D007501:Iron / Q000737:chemistry*; D007700:Kinetics; D009942:Organometallic Compounds / Q000737:chemistry*; D010100:Oxygen / Q000737:chemistry*
D009942:Organometallic Compounds; C066317:ferryl iron; D007501:Iron; D010100:Oxygen