2-Phenoxypyridyl dinucleating ligands for assembly of diiron(II) complexes: efficient reactivity with O(2) to form (mu-Oxo)diiron(III) units.

A series of 2-phenoxypyridyl and 2-phenoxyimino ligands, H(2)L(R,R') [2,2'-(5,5'-(1,2-phenylenebis(ethyne-2,1-diyl))bis(pyridine-5,2-diyl))diphenol, where R = H, Me, or t-Bu, and R' = H or Ph] and H(2)BIPS(Me,Ph) [(3,3'-(1E,1'E)-(3,3'-sulfonylbis(3,1-phenylene)bis(azan-1-yl-1-ylidene))bis(methan-1-yl-1-ylidene)bis(5-methylbiphenyl-2-ol)], were synthesized as platforms for nonheme diiron(II) protein model complexes. UV-vis spectrophotometric studies and preparative-scale reactions of L(R,R') or BIPS(Me,Ph), where L(R,R') and BIPS(Me,Ph) are the deprotonated forms of H(2)L(R,R') and H(2)BIPS(Me,Ph), respectively, with iron(II) revealed that the presence of sterically protective o-phenol substituents is necessary to obtain discrete dinuclear species. The reaction of L(Me,Ph) with iron(II) in tetrahydrofuran (THF) afforded the doubly bridged compound [Fe(2)(L(Me,Ph))(2)(THF)(3)] (1), which was characterized in the solid state by X-ray crystallography. A large internal cavity in this complex facilitates its rapid reaction with dioxygen, even at -50 degrees C, to produce the thermodynamically stable [Fe(2)(mu-O)(L(Me,Ph))(2)] (2) species. Reaction of (18)O(2) instead of (16)O(2) with 1 led to a shift in the Fe-O-Fe vibrational frequency from 833 to 798 cm(-1), confirming the presence of the (mu-oxo)diiron(III) core and molecular oxygen as the source of the bridging oxo group. The L(Me,Ph) ligand is robust toward oxidative decomposition and does not display any reversible redox activity.