An Advanced Inorganic Laboratory Experiment Using Synthesis and Reactivity of a Cycloheptatriene Molybdenum Complex

Francis J. Timmers Dow Chemical Company, 1776 Building, Midland, MI 48674 . William F ~ a c h o l t z ' University of Wisconsin-Oshkosh, Oshkosh, W 54901 I Since ferrocene was first proposed a s a sandwich compound in 1952, the field of organometallic chemistry has experienced explosive growth. Complexes between transition metals and unsaturated organic compounds have become ubiquitous to this area of chemistry ( I ) . These unsaturated organic fragments bond to the transition metal such that the n-electrons of the organic moiety donate to an empty metal d-orbital to form a o-bond. Concurrently, a set of electrons in filled metal d-orbitals donate to the empty n-antibonding orbitals of appropriate symmetry on the or) ganic ligand to form n-bonds (Fig. 1 . Because the n-electrons of the organic group become the o-bond i n the complex, t h e s e m a t e r i a l s frequently a r e referred to a s n-complexes. The notation 11" is used to describe the number of atoms, x, coordinated to the metal center in a n-complex. Organic ligands of this type are referred to a s o-donor and n-acceptor ligands. The degree of a-donating and n-accepting ability of the ligand greatly affects the electron density (and, therefore, reactivity) a t both the organic moi'Author to whom correspondence should be addressed. ety and the metal center. For this reason n-complexes remain a n intense area of study as stoichiometric reagents in organic synthesis and in catalysis applications. There is, however, a paucity of advanced inorganic laboratory experiments that address the synthesis, characterization and reactivity of n-complexes and many that do exist deal with ferrocene and its derivatives. One reason for this problem is the lack of relevant experiments that can be performed within a reasonable laboratory time frame. The reactions in the laboratorv e x ~ e r i m e n t described herein involve the synthesis, reactivity, and characterization of (n6-cycloheptatriene) molybdenum tricarbonyl, (I~'-C~H~)MO(CO)~. Isolation and characterization of all major products are desipned to be accomplished within two lahoratorj periods itoial time 7 11,. ~ h rcactions inc vol\~cd this c:xoerim(!nt are .iumrnarized in Firrurr 2. The in first reaction is the synthesis of (q6-cycloheptatriene)molybdenum tricarbonyl, (q6G7HB)M~(C0)3, through the direct reaction of molybdenum hexacarbonyl, Mo(CO)~, with cycloheptatriene. The second reaction is the formation of

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[(q7-cycloheptatrienyl)molybdenum tricarbonyll hexafluorophosphate, [(q7-C7H7)Mo(C0)31[PF61. This transformation is done by hydride abstraction using the triphenylcarbenium ion. (q7-cycloheptatrienyl)iodomolybdenum dicarbonyl, (q7-C7H7)Mo(CO)zI,s synthei sized in the third reaction by substitution of CO by 1- in [(q7-C7H7)Mo(C0)31+. substitution reaction is a n in The situ NMR tube reaction that increases the number of experimental techniques to which the student is exposed in this laboratory experience. The experimental procedures described herein are different from those reported in the literature ( 2 4 ) in that they are simpler to perform and t a k e u p much less time. The synthesis and characterization of the primary product are completed in the first

nCamplex Orbitals

'<&,'
0

Figure 1. Molecular orbital diagram for a metal-olefin n-complex.

) )3 Figure 3. 'H N M R spectra for ( q 6 - ~ 7 ~ , ) ~ o((A~ ,0 [(I$ C7H7)Mo(CO),I[PF6I ( I I ~ - C ~ H ~ ) M OC )CNote: I (B), ( ( . O ) ~ Peaks observed at 2.2 ppm in B and C, and at 7.2 in A are due to residual protons in the acetone-d6 and chloroform-d3, respectively. Other peaks in the spectrum are due to a small amount o free cycloheptaf triene. laboratory period with the remainder of the experiment finished in the second period. These experiments involve inert atmosphere techniques including "flash" column chromatography under nitrogen, and the use of IR, 'H and 3C NMR spectral analysis to characterize the products. These experiments also can help to launch a discussion on concepts developed in lecture. These include substitution mechanisms, aromaticity, assignment of oxidation states, electron density changes a t the metal, coupling in 'H NMR and 2-D NMR techniques and the use of group theory to explain the number of observed bands in the IR spectra.

Figure 2. Reactions of the cycloheptatriene molybdenum complexes

Experimental The reagents for this experiment are priced reasonably depending on quantities purchased. Cycloheptatriene (Aldrich, =$15.00/100mL) should be freshly distilled prior to the laboratory for best results. Molybdenum hexacarbony1 (Aldrich, =$22.00/10 g) and triphenylcarbenium hexafluorophosphate (Aldrich, =$30.00/10 g) can be used as received. All other reagents and solvents were used a s received. All reactions were carried out under a blanket of nitrogen. 'H and 13C NMR spectra were obtained on a JEOL GSX270 spectrometer a t am-

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Journal of Chemical Education

bient temoeratures. Chemical shifts are exoressed a s nom u m n by t h e addition of n i t r o g e n - s a t u r a t e d dichlodownlield of inrernal TMS followad by n ~ u l t i ~ l i c i t ; . ' ~ ~romethane, CH2ClZ.The product was collected in a presoectra were ohrained on n Mattion Polaris Fourier Transweighed 100-mL round-bottomed flask. The solution was f i r m Infrared spectrometer using either KBr solution concentrated on a rotary evaporator under reduced pressure with the last traces of solvents being removed in cells, or CaFz solution cells whenever bexafluorophosphate vacuo. The typical yield for students in our experiences is salts were present. Isolated products are only moderately approximately 3045%. The red solid was stored under niair sensitive. They can be handled briefly in air or under a nitrogen blanket but they should be stored under nitrogen. trogen. No more than 25% of the isolated solid should be used for NMR and IR analyses. Solvent choices include henzene-d6, chlorofom- d3, CCI.,, and CSz. 'H NMR (C6D6) (q6-~ycloheptatriene)rnolybdenum tricarbonyl, 6 2.45 (m), 3.00 (m), 3.60 (p),4.92 (m), and 5.2 (m) ppm. 13C (TI~-C~H~MO(CO~ NMR (C6Ds)6 102.7, 97.2, 60.2, 27.2 ppm. CO carbons are observed a t 216.1 pprn a s a very small broad peak. IR (benMO(CO)~ g, 3.8 mmole) was added to cyclohepta(1.0 zene) uco 1984,1915, and 1887 cm-'. triene (4.0 mL, 38 mmole) in 10 mL of nonane and heated to reflux for 2 h with stirring. (The limit to higher yields in [(q7-~yclohep~atrienY~)rnQlybdenurn iricarbonyl] this reaction is believed to be due to the sublimation of the nexafluorophosphate,[(II - C ~ ~ ~ ~ / M O ( C ~ ) ~ / [ P F F , / MO(CO)~ away from the reaction mixture. As noted in other sublimes published syntheses (5),this unreacted MO(CO)~ Approximately 75% of the product obtained in the first into the condensor and must be pushed back manually into synthesis was weighed and then dissolved in 15 mL of the reaction mixture to maximize the yield over shorter CHzClz. To this solution was added a n equimolar quantity of triphenylcarbenium hexafluorophosphate, reaction times. We use a long spatula for this purpose. An alternative method that also produces an increase in the [(CGHS)BCI[PFBI. yields is to wrap the hose that feeds cold water to the conCaution: Handle this solid and solutions with the densor around the unheated top of the reaction flask. This triphenylcarbenium ion present with gloves. leads to the subliming of the Mo(C0)e to occur a t the upper The solution was stirred a t room temperature for 30 surface of the round-bottomed flask rather thanin the conminutes. The solution was vacuum filtered, washed with 3 densor. Agitation of'the reaction mixrun! (!asily washes the sublimed mntrrinl back intu the reaction solution.^ The sox 5 mL of CH2Cl2,dried in vacuo, and collected (80-90% lution was then cooled to room temperature under nitroyield). 'H NMR (acetone-ds) 6 6.6 (s) ppm. I3C NMR (acegen. The reaction mixture was passed through a 3 in. x 1 tone-d,J 6 101.8 pprn (CO carbons not observed). IR (acein. dry plug of neutral alumina using nitrogen gas to push tone) uco 2076 and 2028 cm-'. the solvent quickly through the plug. The column was then (~7-~ycloheptatrieny~)iodornolybdenurn dicarbonyl, washed with 3 x 10 mL of nitrogen-saturated ligroin to (q 7 - ~ ~ h ? ) ~ o ( ~ 0 h l elute nonane, unreacted cycloheptatriene, and unreacted MO(CO)~. orange product was removed from the colThe This preparation was carried out in situ in a n NMR tube. Approximately 25% of the product from the previous reaction, [q7-C~H~)MO(CO)~I[PF~I, was placed in a n NMR tube and dissolved in acetone-ds. A 'H NMR spectrum was obtained. To the NMR tube a few small crystals of sodium iodide were added. The solution turned dark green quickly and gas evolution was observed. A 'H NMR spectrum was obtained. Several drops of the solution from the NMR tube were removed and diluted with acetone. The IR spectrum was obtained on the resulting solution using acetone as the reference. Yield is quantitative by 'H NMR spectroscopy. 'H NMR (acetone-ds) 6 5.7 (s) ppm. 13C NMR (acetoned6) 6 95.7 pprn (CO carbons not oberved). IR (acetone) vco 2011 and 1963 cm-'.
Results and Discussion

Figure 4.2-D NMR 'H-'H COSY for (q6-C,H~)MO(CO),.

'H NMR spectra for the n-complexes synthesized in this experiment are shown i n Figure 3. (q6-C~HB)MO(CO)~ exhibits five distinct complex multiplets centered a t 2.45, 3.00, 3.60,4.92, and 6.05 ppm, all exhibiting the proper integration. These are associated with the five unique type of hydrogens on the q6-cycloheptatriene ligaud. The endo and exo hydrogens on the sp3 carbon atom of the ligand have similar chemical shifts and cannot be resolved on lower field instruments but are observable on the 270 MHz JEOL NMR. The homonuclear correlated 2-D 'H spectrum of
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spectra (Fig. 5) allow for analysis of the number of observed stretches as related to their simplified symmetry. (q6-C7Hs)Mo(C0)3 has pseudo C, symmetry and, employ7, ing group theory ( 1 is predicted to exhibit three bands a s i s observed a t 1984, 1915, 1 8 8 7 cm-'. T h e (q7C,H7)Mo(C0)3 cation h a s pseudo Cav symmetry if t h e tropylium cation is treated as a flat circular plate. Theory predicts that two CO stretches should be observed and two bands are observed a t 2076 and 2928 cm-I. Finally, (q7C ~ H ~ ) M O ( C O ) ~pseudo C, symmetry and group theory has I predicts two CO stretches. Two stretches are observed a t 2011 and 1963 cn-I. The change in frequency of the CO stretches also reflects the chanee in electron densitv a t the metal. Like nligands, CO i s a o-donor and a n-acceptor. The CO bond order is reduced when the metal can n-donate into a C-0 n-antibonding orbital; since the CO-stretching frequency reflects the CO bond order, the uco is reduced. Although hydride abstraction from the cycloheptatriene ligand in (q6-C7H8)Mo(C0)3 not a formal oxidation of the metal, is the CO stretches i n the product, [q7-C7H7)Mo(CO)d+. move to higher frequencies. This fact reflects that the tropylium ligand is a poorer o-donor and a better rr-acceptor than the cycloheptatriene ligand, thereby either pushing less electron density to the metal or pulling more electron density away from the metal. Once again, when 1- substitutes CO in Kq7-C7H7)Mo(CO)dtto give (q7-C7H7)Mo(C0)21, forno mal reduction of the metal occurs. However, uco moves to lower frequencies. I t was pointed out above that the anionic iodide, a n-donor, replaces the neutral CO, a n-acceptor. Not only i s there less competition for n-electron density from the metal (two CO ligands rather than three), a n-donor ligand i s now present a s well.
Discussion Questions 1. Why was nanane chosen as the solvent far the first reaction rather than hexane, for example? 2. What features about the triphenylcarbenium cation lead to its observed reactivity? 3. Write out balanced reactions that show haw you could remake (~f-C~H,)Mo(CO)~from [T,~-C~H~)MO(CO)~]+. 4. What is the oxldatian state of molybdenum (Mo) in each complex? 5 . Design a set ofexperiments (with balanced equations)that would allow you to determine whether it is the exoar enda hydrogen that is abstracted in the first reaction. Assume that the most upfield signal in the 1H NMR spectrum of ( $ - C 7 ~ s ) ~ o ( C 0 ) 3 e m hydrogen. is the Acknowledgment W. F. W. would like to thank the NSF Instrumentation a n d L a b o r a t o r y I m p r o v e m e n t P r o g r a m ( g r a n t ILI9153034) for partial support to purchase the JEOL NMR spectrometer and the College Science Instrumentation Program (grant CSI-8750071) for partial support to purchase the Mattson polaris FT-IR spectrometer. A special thanks to C. Gibson for his helpful comments and suggestions. Literature Cited
1 Collman. J. P.; . Hegedus, L. S.; Norton. J. R.: Finke. R. G. P?i,icipie.3 andApplieolrons ~fors~~imnairimo chemistry: university science ~ o o k s M;II valley. ~et i : CA, 1987. 2. Dauben. H J.; Honnen, L. R J Am. Chrm. Soc 1958.80.5570. . 3. Kmg. R. 6. I" orgonomatoiiic Synth~sis. d 1 Eiseh, J. J.;Kng, R. B., Ed.: A c a ~ V : demie Press:New York, 1965;pp 125-126 and 140-1M. 4. Angeliei. R. J. In Synthesis and Techniques m Inorganic Chemistry, 2nd ed., Univer~ sify Science Books: MiilValley. CA. 1986: Erpenment 14. 5. Angeli", R. J. InReosents for %)ansition Metal Complrr nnd Orgonomelallrc Synlhere$, Inorganic Syn. Val. 28; Angelici, R. J.. Ed.:Wiley: New York, 1991; pp 4547. 6. Morris. 0.A. MagnrlicR~sononn Chemistry 19R6.24, 371. in 7. Cotton. F. A. Ch~mimlApplieotions ofGrnup Tksory: 3rd ed.: Wiley: New York, 1990.

Uavenumbers (cm-I1

There are sevirai good pling'between t h e various references outlininrr the inter~retation 2D NMR results of (61, which will not be elaborated on here. When t h e hydrogen a t o m i s a b s t r a c t e d from (q6C7H6)M~(C0)3, aromatic tropylium ligand is generated the and all sites become chemically equilvalent on the NMR time scale a t room temperature. This results in a singlet a t 6.6 ppm for the Kq7-C7H7)Mo(C0)31 cation. The observed chemical shift and multiplicity demonstrates the aromatic nature of the ligand. When a n 1-replaces a CO, the neutral complex (q7-C7H7)Mo(C0)21 formed. The singlet a t 5.7 is ppm confirms that the aromatic nature of the n-ligand is retained. The fact that the signal moves upfield a s a result of this substitution is consistent with more electron density being available a t both the metal and n-ligand in this complex. (The anionic iodide is a n-donor and replaces the neutral CO, a n-acceptor.) The number and freauencv of the CO-stretchine bands observed in the IR spe&a o? the complexes demlnstrate the changes i n svmmetrv and electron densitv a t the metal center a s a resilt of the various transforma"tions. The IR

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Journal of Chemical Education