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New polynuclear compounds of iron(II) chloride with oxygen donor ligands Part II. Polymeric [FeCl2(OPMe3)]∞ and mononuclear FeCl2(OPMe3)2. Syntheses, properties and single crystal structure determinations

1991; Elsevier BV; Volume: 184; Issue: 2 Linguagem: Inglês

10.1016/s0020-1693(00)85068-9

1873-3255

F. Albert Cotton, Rudy L. Luck, Kyung-Ae Son,

Organometallic Complex Synthesis and Catalysis

Abstract A new polymeric Fe(II) chloride complex, [FeCl2(OPMe3)]∞ (1), has been synthesized from the reaction of stoichiometric quantities of FeCl3, Fe and OPMe3 (2:1:3) in THF. Use of a 2:1:6 ratio in the above reaction gives instead the mononuclear complex FeCl2(OPMe3)2 (2). The structure of the polymer consists of infinite chains of FeCl2(OPMe3) units, where each Fe atom is linked by four bridging chlorine atoms to two other Fe atoms. The arrangement of the four chlorine atoms and one OPMe3 molecule around the iron atom results in a trigonal bipyramidal coordination geometry. Complex 2 has tetrahedral geometry. The magnitudes of the magnetic moments for 1 and 2 at room temperature are 4.90 and 5.51 BM, respectively, indicative of high spin Fe2+. In 1, two different Fe…Fe distances 3.560(0) and 3.688(0) A alternate along the chain, the FeCl bond distances are in the range 2.35–2.60 A, the FeO distance is 1.954(2) A and the PO distance is 1.513(2) A. In 2, the FeCl distances average to 2.291(4) A, the average FeO and PO distances are 1.994(2) and 1.504(1) A, respectively. Crystallographic data: 1, monoclinic, space group P21/n, a=6.810(2), b=12.943(5), c=9.645(2) A, β=100.224(2)°, V=836.6(11) A3, Z=4, R=O.041 (Rw=0.058) for 101 parameters and 1665 unique data having Fo2>3σ(Fo2). 2, orthorhombic, space group P212121, a=11.270(3), b=12.011(2), c=10.811(2) A, V=1463.5(5) A3, Z=4, R=0.052 (Rw=0.064) for 142 parameters and 1356 unique data having Fo2>3σ(Fo2).