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Synthesis and Structural Characterization of Iron(II) Complexes with Tris(imidazolyl)phosphane Ligands: A Platform for Modeling the 3‐Histidine Facial Triad of Nonheme Iron Dioxygenases
Author(s) -
Bittner Michael M.,
Baus Jacob S.,
Lindeman Sergey V.,
Fiedler Adam T.
Publication year - 2012
Publication title -
european journal of inorganic chemistry
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 0.667
H-Index - 136
eISSN - 1099-0682
pISSN - 1434-1948
DOI - 10.1002/ejic.201101282
Subject(s) - chemistry , tris , dioxygenase , stereochemistry , histidine , carboxylate , substrate (aquarium) , molecule , enzyme , organic chemistry , biochemistry , oceanography , geology
Several monoiron(II) complexes containing tris(imidazolyl)phosphane (TIP) ligands have been prepared and structurally characterized by using X‐ray crystallography and NMR spectroscopy. Two TIP ligands were employed: tris(2‐phenylimidazol‐4‐yl)phosphane (4‐TIP Ph ) and tris(4,5‐diphenyl‐1‐methylimidazol‐2‐yl)phosphane (2‐TIP Ph2 ). These tridentate ligands resemble the 3‐histidine (3His) facial triad found recently in the active sites of certain nonheme iron dioxygenases. Three of the reported complexes are designed to serve as convenient precursors to species that model the enzyme–substrate intermediates of 3His dioxygenases; thus, each contains an [Fe(κ 3 ‐TIP)] 2+ unit in which the remaining coordination sites are occupied by easily displaced ligands, such as solvent molecules and/or carboxylate groups. The viability of these complexes as precursors was demonstrated through the synthesis of TIP‐based complexes with β‐diketonate and salicylate ligands that represent faithful models of β‐diketone dioxygenase and salicylate 1,2‐dioxygenase, respectively.