Syntheses and crystal structures of two new cationic 3,5-dimethylpyrazole derivatives containing organoiron mixed-sandwiches as substituent groups

[η6-1-Chloro-2-(pyrrolidin-1-yl)benzene](η5-cyclopentadienyl)iron(II) hexafluoridophosphate and (η5-cyclopentadienyl){2-[η6-2-(pyrrolidin-1-yl)phenyl]phenol}iron(II) hexafluoridophosphate

“…In the title complex salts, [ 6 -1-chloro-2-(pyrrolidin-1-yl)benzene]( 5 -cyclopentadienyl)iron(II) hexafluoridophosphate, (I), and ( 5 -cyclopentadienyl){2-[ 6 -2-(pyrrolidin-1-yl)phenyl]-phenol}iron(II) hexafluoridophosphate, (II), the Fe ion is located at distances of 1.644 (4) and 1.663 (1) Å from the Cp plane, and at distances of 1.554 (4) and 1.557 (1) Å from the benzene ring plane, respectively. These values are close to those reported in the literature for similar complexes (see, for example, Pió rko et al, 1995;Fuentealba et al, 2007;Manzur et al, , 2009Hendsbee et al, 2010, and references therein).…”

“…The N atoms in both complexes show similar bond lengths to ring atom C2 [1.344 (11) Å for (I) and 1.356 (4) Å for (II)] and to the methylene C atoms of the pyrrolidine rings [range 1.476 (4)-1.484 12 which is in agreement with the C ar -Nsp 2 bond length (Allen et al, 1987), implies that depyramidalization of the N atom takes effect in both complexes. This suggestion is corroborated by the geometry around the N atom; the sum of angles is close to 360 in each complex [358.4 (9) and 357.1 (4) , respectively, in (I) and (II), and this may, as discussed by Manzur et al (2000), result from a partial delocalization of the N1 lone pair of electrons toward the complexed benzene ring.…”

“…Similar values, viz. 6.0 (5) and 7.1 (6) , have been reported for phenylhydrazine complexes studied by Manzur et al (2000). The pyrrolidine ring of (I) in the solid state adopts a twisted conformation with C12 and C13 located out of the plane defined by the remaining three atoms.…”

“…The distances from atom Fe1 to atom C2, which carries a pyrrolidin-1-yl substituent in both complexes, are among the largest reported for similar complexes, along with the value of 2.252 (2) Å reported previously for one of the substituted ring C atoms of a dipyrrolidinyl complex (Jenkins et al, 2009). Other reports with similar Fe-C subst distances include the structure of an Fe(Me 5 Cp)phenoxide-water complex [C subst bonded to O; 2.269 (9) Å ; Moulines et al, 1995;Djakovitch et al, 1996], a pmethylphenylhydrazine FeCp fragment in a tungsten complex [2.24 (1) Å ; Ishii et al, 1994] and an N 0 -isopropylidene hydrazone of p-methylphenylhydrazine [2.201 (5) Å ; Manzur et al, 2000]. Many of the Cp and pentamethyl-Cp complexes examined in a series of studies by Carrillo and coworkers (see, for example, Fuentealba et al, 2007;Manzur et al, 2000Manzur et al, , 2007Manzur et al, , 2009 have an Fe-C subst (bonded to N) distance shorter than that found in our work.…”

(η5-Cyclopentadienyl)(η6-1,2-dipyrrolidin-1-ylbenzene)iron(II) hexafluoridophosphate

“…For the synthesis of the title compound and related structures, see: Lee et al (1989). For the crystal structures of {( 5 -Cp)( 6arene) Fe(II)} + salts, see: Nesmeyanov et al (1977); Dubois et al (1989); Pió rko et al (1995); Manzur et al (2000); Fuentealba et al (2007); Manzur et al (2009) and literature cited therein.…”