Dramatically Accelerated Selective Oxygen-Atom Transfer by a Nonheme Iron(IV)-Oxo Complex: Tuning of the First and Second Coordination Spheres | Zendy

Leland R. Widger | Zendy; Casey G. Davies | Zendy; Tzuhsiung Yang | Zendy; Maxime A. Siegler | Zendy; Oliver Troeppner | Zendy; Guy N. L. Jameson | Zendy; Ivana IvanovićBurmazović | Zendy; David P. Goldberg | Zendy

Open Access

Dramatically Accelerated Selective Oxygen-Atom Transfer by a Nonheme Iron(IV)-Oxo Complex: Tuning of the First and Second Coordination Spheres

Author(s) -

Leland R. Widger,

Casey G. Davies,

Tzuhsiung Yang,

Maxime A. Siegler,

Oliver Troeppner,

Guy N. L. Jameson,

Ivana IvanovićBurmazović,

David P. Goldberg

Publication year - 2014

Publication title -

journal of the american chemical society

Language(s) - English

Resource type - Journals

SCImago Journal Rank - 7.115

H-Index - 612

eISSN - 1520-5126

pISSN - 0002-7863

DOI - 10.1021/ja410240c

Subject(s) - chemistry , amide , intramolecular force , ligand (biochemistry) , sulfide , sulfoxide , medicinal chemistry , catalysis , crystallography , stereochemistry , organic chemistry , receptor , biochemistry

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.

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