Hexafluorophosphate Salts of Cyclopentadienyliron(II) Complexes of Dibenzodioxin and 1-Methyldibenzodioxin

Abstract

both complexes, O--C bonds of the coordinated ring are shorter than those of the uncoordinated ring. CommentThe title complexes were synthesized, following a previously described procedure (Sutherland, Pi6rko, Gill & Lee, 1982), by the reaction of catechol with (r/6-1,2 -dichlorobenzene)(r/5-Cp)iron(II) hexafluorophosphate and with (r/6-2,3-dichlorotoluene)(r/5-Cp)iron(II) hexafluorophosphate to give (1) and (2), respectively. Crystals of both complexes were grown from acetone-Michloromethane-diethyl ether solutions at ca 255 K. Crystals of complex (2) contain molecules of diethyl ether in the complex:solvent ratio 2:1. Results obtained in the course of this study add to earlier studies on the synthesis, reactivity and, in particular, the structure of tricyclic heterocycles complexed with an FeCp moiety. It had been noted earlier that the effect of complexing iron, the presence of substituents on the heterocycle and the packing forces in the crystal all may influence the overall geometry of the heterocycle. Our results provide additional information on the influence of the above factors on the structure of the heterocycle.

(η5-Cyclopentadienyl)(η6-phenoxathiin 10,10-dioxide)iron(II) hexafluoridophosphate and phenoxathiin 10,10-dioxide

“…The C-O distances, however, are quite different, as the bond extending from the bridging O atom to the C atom of the coordinated ring is significantly shorter than the C-O bond extending towards the uncoordinated ring [1.361 5and 1.393 (5) Å , respectively]. Both these observations agree with earlier findings for phenoxathiin and azaphenoxathiin complexes (Lynch et al, 1986;Sutherland et al, 1988) and for dibenzodioxin complexes (Pió rko et al, , 1995Hendsbee et al, 2010).…”

“…The earlier studies of the synthesis and structure of dibenzodioxin and thianthrene FeCp complexes suggested that only FeCp-in-fold molecules are formed in such a reaction. This conclusion was based on the results of several crystallographic studies (Simonsen et al, 1985;Abboud et al, 1990;Christie et al, 1994;Pió rko et al, 1994Pió rko et al, , 1995. Recently, we reported that a double nucleophilic substitution reaction leading to the formation of (1,2,3,4,4a,10a-)-1-methylthian-threne FeCp hexafluoridophosphate gave rise to a mixture of both in-fold and out-of-fold isomers, as found in a crystallographic study of the reaction products (Hendsbee et al, 2009).…”

(η5-Cyclopentadienyl)[(1,2,3,4,4a,10a-η)-1-methylthianthrene]iron(II) hexafluoridophosphate acetone 0.33-solvate

“…The distances from the Fe ion to the Cp plane and to the complexed benzene ring plane are 1.666 (3) and 1.537 (3) Å , respectively, in molecule A, 1.662 (3) and 1.551 (3) Å in B, and 1.648 (4)/1.538 (3) and 1.701 (4)/1.538 (3) Å in the two disorder components of the Cp ring in C. These values are close to those reported in the literature for similar complexes (see, for example, Lynch et al, 1986;Abboud et al, 1990;Pió rko et al, 1995;Fuentealba et al, 2007;Manzur et al, 2007;Jenkins et al, 2008).…”

“…The complexed Cp and benzene rings of (I) are nearly coplanar in all three molecules, with a dihedral angle of 0.2 (5) for molecule A, 2.8 (5) for B, and 2.19 (4) and 6.86 (6) for the disordered Cp ring in C. These values are in the range observed for other thianthrene and dibenzodioxin FeCp complexes in our previous studies (see, for example, Simonsen et al, 1985;Lynch et al, 1986;Abboud et al, 1990Abboud et al, , 1991Christie et al, 1994;Pió rko et al, 1995). The Cp-Febenzene ring centroid vectors are nearly collinear, with angles of 179.65 (8) and 178.42 (7) for molecules A and B, and 178.69 (7) and 176.39 (7) for the disordered Cp ring in C. These values are typically found in the literature for FeCparene complexes (see, for example, Manzur et al, 2000;Fuentealba et al, 2007).…”

“…This is the first time that the formation of both FeCp-out-of-fold and FeCp-in-fold molecules of folded tricyclic heterocycles resulting from a double nucleophilic aromatic substitution reaction have been observed. Our earlier studies of the synthesis of dibenzodioxin and thianthrene FeCp complexes using the same reaction suggested that only FeCp-in-fold molecules are formed in such a reaction, as crystals of the dibenzodioxins and thianthrenes studied by X-ray crystallography have shown the presence of only FeCp-in-fold species (Simonsen et al, 1985;Abboud et al, 1990Abboud et al, , 1991Christie et al, 1994;Pió rko et al, 1994Pió rko et al, , 1995. Conversely, phenoxathiin complexes obtained in a similar reaction have shown the presence of only out-of-fold molecules in the solid state, as determined from examination of their crystal structures (Lynch et al, 1986;Sutherland et al, 1988).…”