Boletín de la Sociedad Chilena de Química
versión impresa ISSN 0366-1644
Bol. Soc. Chil. Quím. v.44 n.3 Concepción set. 1999
OBSERVATION OF STABLE 17 e IRON(III) CYCLOPENTADIENYL
Departamento de Química, Facultad de Ciencias, Universidad de Chile, Casilla 653,
(Received: April 27, 1999 - Accepted: June 14, 1999)
The EPR spectra of a series of mononuclear complexes [CpFe(dppe)SR]PF6 R = C6H5 (1), C3H7 (2), p-C6H4Br (3) and the binuclear [CpFe(dppe)-S-CH2CH2-S-CpFe(dppe)](PF 6)2 (4) were measured. All the paramagnetic complexes exhibit intense signals in both solid state as well as in CH2Cl2 solution. Analysis of the spectra indicates a pseudooctahedral structure for the complexes except for complex (2) for which a tetragonal distortion in solid state was observed. Some degree of delocalization of the unpaired electron for (3) and (4) was suggested. The stabilization of the radicals by the thiolate ligands is discussed.
KEY WORDS: Iron-sulfur complexes, EPR, organometallic radical, thiolate compounds.
Se midieron los espectros EPR de una serie de complejos mononucleares [CpFe(dppe)SR]PF6 R = C6H5 (1), C3H7 (2), p-C6H4Br (3) y del complejo binuclear [CpFe(dppe)-S-CH2CH2-S-CpFe(dppe)](PF 6)2 (4). Todos los compuestos paramagnéticos muestran intensas señales tanto en estado sólido como en solución de CH2Cl2. El análisis de sus espectros indica una estructura pseudooctaédrica para los complejos, excepto para el compuesto (2) en estado sólido el cual muestra una distorsión tetragonal. Un cierto grado de deslocalización del electrón desapareado para los compuestos (3) y (4) es sugerido. Se discute la estabilización de los radicales por ligante tiolato.
PALABRAS CLAVES: Complejos hierro-azufre, EPR, radicales organometálicos, compuestos tiolatos.
Although organotransition metal chemistry has long been dominated by complexes of obeying the so-called the 18-electron rule1), several examples of compounds having 17 2) or 19 3) electron have appeared in the literature. In spite of that 19 4) or 17 e 5) complexes are usually unstable and hence they are isolated only in solution or detected as transient species in the last time numerous stable compounds of these type have been reported6).
Organometallic 17e complexes of iron(III) are particularly scarce, although coordination iron 17e compounds are common.
It appears to be that the stabilization of organometallic iron 17e complexes require two conditions:
i) The presence of ligands around the iron atom, having bulky substituents.
ii) Ligands s or p donor, to compensate the +3 formal oxidation state of the iron.
Consistently with this, species [CpFe(CO)2R]·+ are believed to be transient intermediate generally too unstable to be detected2,7). On the other hand substitution of CO by a bulky diphosphine as Ph2P(CH2)2PPh 2, (dppe) as well as most s donor ligand and substitution of Cp by Cp* (C5Me5) leads to stable paramagnetic [Cp*Fe(dppe)R]·+ compounds5). We have previously reported the formation of stable Fe(III)-thiolate 17e complexes from the oxidative addition of dithioethers as well as on thiols to the fragment CpFe(dppe)+ (scheme 1)8-13). Here we report a EPR characterization of such organometallic radicals. The first example of stable containing the unsubstituted C5H5 ring.
We have selected from the series [CpFe(dppe)SR]PF610-12) one representative of each type: compound (1) having a phenyl substituent linked to the sulfur atom complex (2) has an aliphatic substituent bond to the sulfur atom, compound (3) has a para-substituent heavy atom in the phenyl ring and complex (4) a binuclear Fe(III)-Fe(III) bridged thiolate.
RESULTS AND DISCUSSION
Room temperature CH2Cl2 solutions of complexes (1) and (2) have symmetric one single peak. In the EPR spectra these features are similar to that observed for the solution EPR spectra for similar [CpFe(diphos)R]+ complexes diphos = diphosphine, R = alquil, C = CR6c).
The EPR spectrum of (1) is shown in Figure 1 and values are displayed in Table I. As expected the EPR lines in solution are sharp indicting an average anisotropies in both, the g tensor and the nuclear coupling due to the rapid tumbling in solution14). On the contrary the EPR spectra of (3) and (4) in CH2Cl2 solution appears most broad as is shown in Figure 1 for (3). In the case of (3) the broadening can be due to an unresolved hyperfine coupling of the bromine atom15).
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aAt room temperature; bCH2Cl2; cHalf linewidth values in parenthesis.
On the other hand, the some broad signal observed for 4 can be due to the electron exchange between the two iron atoms in the binuclear complex. Similar broadening of the EPR signal was observed in the spectrum of [CpFe(dppe)-S-C6H4N-Fe(Cp((dppe)](PF 6)216), and also int he spectrum of the binuclear complex [Cp*Fe(dppe)-CC-C6H4-CC-Fe(dppe)Cp *][PF6]217). The g values are some higher than those of the free electron value(g=2.0023) as usually observed for 17 electron iron(III) compounds having a single occupied HOMO with a predominant metallic character5c).
FIG. 1. EPR spectra of complexes (1) and (3) in CH2Cl2 solution at room temperature.
Owing to the high stability of the complexes (1)-(4) in solid state we have measured the EPR spectra directly of the solid samples. The spectra of complexes (1), (3) and (4) exhibit a single one signal, sharp for (1) and broad for (3) and (4), at g values similar to that observed in solution (see Figure 2). Lacking hyperfine splitting, the spectra of these compounds cannot delineate the precise orbital makeup of the SOMO (semioccupied MO) but they do not indicate that the radical retains the approximate octahedral symmetry18), since lower symmetry would lead to a splitting of the g-tensor.
On the other hand for (2) the expected two g-tensor component for an axially symmetric was observed (Figure 2).
No phosphorus hyperfine splitting in any of the g components of the spectrum is observed, indicating no interaction of the unpaired electron with the phosphorus atom around the metal center. The g values are greater than 2, which suggest that the unpaired electron is located in a predominantly metal (iron(III)), low spin d5 orbital.
This in consistently with MO calculation for the similar organometallic radicals [Cp*Fe(dppe)R]+ where the single occupied HOMO is 52%, localized on the metal5c). This is also in agreement with the low chemical reactivity exhibited by these radicals. Similarly to data in solution the solid spectra of (3) exhibits a most broad signal which suggest some probable unresolved splitting hyperfine through the bromine atom. Consistently with this the hyperfine coupling constant for bromine in Ru-Br complexes is 120 G 19), similar to the half linewidth for (3), see Table I. For complex (4) as mentioned previously, the broadening can be due to an exchange interaction of the unpaired electron between the two centers in the binuclear complex (4) see Figure 3.
FIG. 2. EPR spectra of complexes (1), (2) and (3) in solid state at room temperature.
FIG. 3. EPR spectra complex (4) in solution (A) and in solid (B).
Our early electrochemical studies on the complexes [CpFe(dppe)-SR]PF613) showing that the reduction Fe(III) Æ Fe(II) is an iron centered process also confirm the present EPR results.
To our best knowledge this EPR characterization constitutes the only one EPR study of stable low spin d5, Fe(III) complexes containing the unsubstituted cyclopentadienyl ring22). We believe that the stability of the CpFe(dppe)SR+ radical complexes compared with those of [Cp*Fe(dppe)R]± can be due to soft and polarizable thiolate ligand which stabilizes the formation of the Fe(III) complex compensating the high positive charge of the iron.It is also interesting to note the easily of the EPR measurement in solid state which will be useful in the study of future intercalation solid state reactions containing these radical species.
[CpFe(dppe)SR]PF6 complexes were prepared as described previously8-10). Solution freshly prepared by dissolving the solid sample in CH2Cl2 and degassed with nitrogen were used. Its EPR spectrum was immediately recorded using a Brucker ECS 106 spectrometer using a rectangular mode cavity with a 50 Hz field modulation. The measurements were made with the microwave band X (9.79 GHz). For the solid sample the crushed powder was used.
We are grateful to DID U. de Chile (Project 98-018) and FONDECYT (Project 198-1082) for financial support.
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