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Dinuclear and Hexanuclear Iron(III) Oxide Complexes with a Bis(bipyridine) Ligand: A New [Fe(6)(&mgr;(3)-O)(4)](10+) Core
Craig M. Grant1, Michael J. Knapp, William E. Streib
1Department of Chemistry and Molecular Structure Center, Indiana University, Bloomington, Indiana 47405-4001, and Department of Chemistry, University of California at San Diego, La Jolla, California 92093-0358.
Abstract:
The use of the bis(bipyridine) ligand L (1,2-bis(2,2'-bipyridyl-6-yl)ethane) has yielded new dinuclear and hexanuclear complexes. The FeCl(3)/NaO(2)CPh/L (4:4:1) reaction system in MeCN gives red-brown [Fe(6)O(4)Cl(4)(O(2)CPh)(4)L(2)][FeCl(4)](2) (1). The same reaction system in a 3:3:1 ratio in MeOH gives orange [Fe(2)(OMe)(2)Cl(2)(O(2)CPh)L][FeCl(4)] (2). Complex 1.2MeCN: monoclinic, P2(1)/a, a = 15.317(2) Å, b = 18.303(3) Å, c = 16.168(3) Å, beta = 108.91(1) degrees, and Z = 2. Complex 2: triclinic, P&onemacr;, a = 14.099(6) Å, b = 18.510(7) Å, c = 7.108(3) Å, alpha = 96.77(2) degrees, beta = 99.45(2) degrees, gamma = 81.16(2) degrees, and Z = 2. The cation of 1 consists of a near-planar [Fe(6)(&mgr;(3)-O)(4)](10+) core that can be described as three edge-fused [Fe(2)O(2)] rhombs to which are attached two additional Fe atoms. The cation of 2 contains a [Fe(2)(&mgr;-OMe)(2)(&mgr;-O(2)CPh)](3+) core. In both cations, the L group acts as a bridging ligand across an Fe(2) unit, with the bpy rings essentially parallel. Variable-temperature solid-state magnetic-susceptibility studies of 1 and 2 in the 2.00-300 K range reveal that for both complexes the data are consistent with an S = 0 cation and S = (5)/(2) [FeCl(4)](-) anions. These conclusions were confirmed by magnetization vs field studies in the 2.00-4.00 K and 10.0-50.0 kG ranges. Fitting of the data for 2 to the appropriate theoretical equation for an equimolar composition of Fe(2) cations and [FeCl(4)](-) anions allowed the exchange interaction in the cation to be determined as J = -10.5 cm(-)(1) (H = -2JS(1)S(2)) with g held at 2.00. The obtained J value is consistent with that predicted by a previously published magnetostructural relationship.