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NITROGEN REDUCTION

Molybdenum does it again

Richard R. Schrock

Nature reduces dinitrogen under mild conditions using nitrogenases, the most active of which contains molybdenum and iron. The only abiological dinitrogen reduction catalyst that avoids the harsh conditions of the HaberBosch process contains just molybdenum.

mmonia is necessary for all life, because it is the source of nitrogen in essential biomolecules such as proteins and DNA. More than 108 tons per year of ammonia are formed in the environment through reduction of molecular nitrogen in the air by nitrogenase enzymes1,2. A roughly equal amount is formed in the HaberBosch process (at 350550 C and 150350 atm) through reduction of purified nitrogen with hydrogen3; a process that is arguably the most important industrial process discovered in the twentieth century and partially responsible by enabling the production of nitrogen-based fertilizers for a doubling of the population of the earth. It would nevertheless be desirable to reduce molecular nitrogen in a man-made process under milder conditions, because the energy-intensive process demands around 1.5% of the worlds annual energy supply. Discovering such a process would also help us understand how the remarkable and complex catalytic reduction of molecular nitrogen is achieved in naturally occurring nitrogenases. Only one catalytic reduction of molecular nitrogen directly to ammonia is known; the reduction is catalysed by a [HIPTN3N]Mo(iii) catalyst, where [HIPTN3N]3 = {[3,5-(2,4,6-iPr3C6H2)2 C6H3NCH2CH2]3N}3 (ref. 4). The only other abiological catalytic reduction of dinitrogen under mild conditions also employs molybdenum, but yields hydrazine as a primary product, which is then disproportionated into nitrogen and ammonia5. Writing in Nature Chemistry, Yoshiaki Nishibayashi and co-workers describe the second example of a catalytic reduction of dinitrogen selectively to ammonia under mild conditions6, again with a molybdenum catalyst, under conditions similar to those employed in the [HIPTN3N]Mo system, and molecular hydrogen again is the only other product. They find that a Mo(0) dinitrogen complex, [Mo(L)(N2)2]2(-N2) (L is the PNP pincer ligand shown in Fig. 1), on addition of protons (in the form

N2 N

P N N

N2 Mo N

Mo

TfON2 + Me N+ H Me + Co( 5-C5H5)2

P N2

N2 P

Catalyst precursor; P = PtBu2 Toluene, room temperature

NH3

H2

Figure 1 | Dinitrogen is reduced catalytically, by employing lutidinium triflate as the proton source and cobaltocene as the electron source, in toluene at room temperature. The catalyst precursor is a molybdenum(0) dinitrogen complex that contains a PNP pincer ligand. Molecular hydrogen is the only other product.

of 2,6-lutidinium triflate) and electrons (in the form of cobaltocene), catalyses the conversion of dinitrogen to ammonia in toluene with a yield as high as twelve equivalents of ammonia per molybdenum atom. Nishibayashis team proposes that [Mo(L)(N2)2]2(-N2) is cleaved to give one catalytically active molybdenum species and a second catalytically inactive species. The complex [Mo(L)(NNH2)(pyridine) (F)]BF4 is formed on addition of four equivalents of HBF4 in THF to [Mo(L) (N2)2]2(-N2), followed by pyridine. Its isolation and X-ray structural characterization suggests that monomeric species in which molybdenum has been oxidized and dinitrogen reduced are readily formed, although [Mo(L)(NNH2) (pyridine)(F)]BF4 itself is not catalytically active under the chosen conditions. Both Chatt 7 and Hidai8 showed that Mo(0) and W(0) species are oxidized on treatment with acids. No other lutidinium salt is as successful as lutidinium triflate, including [lutidinium]B[3,5-(CF3)2C6H3]4, which was the proton source employed in the [HIPTN3N]Mo system3, so triflate is likely to bind to the oxidized molybdenum atom in intermediates in the catalytic cycle. Cobaltocene (E1/2 = 1.15 V) produces a yield approximately equal to that of decamethylchromocene (E1/2 = 1.35 V), a stronger reducing agent. It was proposed that the reaction takes place at a single metal

centre via reaction intermediates analogous to those proposed first by Chatt 7, several of which were observed in the [HIPTN3N]Mo system. Unfortunately, no catalytically viable intermediates could be isolated or observed in Nishibayashi and colleagues system. Catalytic turnover ceases when the multidentate ligand is lost from the metal in both molybdenum-catalysed systems. The significance of Nishibayashis work is that a quite different type of molybdenum complex (in terms of metal oxidation state and ligand environment) compared with the [HIPTN3N]Mo system is a precursor to a catalyst for the reduction of dinitrogen to ammonia and hydrogen by protons and electrons. As Mo(iii) and Mo(vi) are the minimum and maximum oxidation states observed in the [HIPTN3N]Mo system, it would be reasonable to propose that the minimum and maximum oxidation states of molybdenum in the Nishibayashi system are also Mo(iii) and Mo(vi). Elucidation of the nature of the intermediates will be extremely useful to tease out the essential nature of dinitrogen reducing catalysts. It is satisfying that in the 45 years since the discovery of the first dinitrogen complex, Chatts proposal that dinitrogen can be reduced by protons and electrons on binding to a single molybdenum centre (as opposed to two or more metal centres9,10) has now been demonstrated with a molybdenum catalyst that differs
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significantly in detail from the first catalyst. Abiological catalytic dinitrogen reduction under mild conditions has not been achieved with other metals found in nitrogenases (vanadium and iron)1. The fact is that the difficult process of reducing dinitrogen to ammonia with protons and electrons at room temperature and pressure has been achieved (for the second time) only with a molybdenum-based catalyst. Nishibayashis discovery gives us renewed confidence that other types of molybdenum-based catalysts for this process under mild conditions remain to be discovered. The challenge will be to make reduction of dinitrogen efficient in terms of turnover number, and ultimately to employ more practical sources of electrons and protons.
Richard R. Schrock is in the Department of Chemistry, Massachusetts Institute of Technology, Cambridge, Massachussetts 02139, USA. e-mail: rrs@mit.edu References
1. Burgess, B. K. & Lowe, D. J. Chem. Rev. 96, 29833011 (1996). 2. Eady, R. R. Chem. Rev. 96, 30133030 (1996). 3. Smil, V. Enriching The Earth: Fritz Haber, Carl Bosch, and the Transformation of World Food Production (MIT Press, 2004). 4. Schrock, R. R. Angew. Chem. Int. Ed. 47, 55125522 (2008). 5. Shilov, A. E. Russ. Chem. Bull. Int. Ed. 52, 25552562 (2003). 6. Arashiba, K., Miyake, Y. & Nishibayashi, Y. Nature Chem. 3, 120125 (2011). 7. Chatt, J., Dilworth, J. R. & Richards, R. L. Chem. Rev. 78, 589625 (1978). 8. Hidai, M. Coord. Chem. Rev. 185186, 99108 (1999). 9. Barriere, F. Coord. Chem. Rev. 236, 7189 (2003). 10. MacKay, B. A. & Fryzuk, M. D. Chem. Rev. 104, 385401 (2004).

VIBRONIC COUPLING

Cage-breaking cascade
Philippe C. Hiberty

One-electron oxidation is generally expected to weaken a bond in a molecule or, on rare occasions, break it. Removing one electron from a small propellane cage has now been shown to break three lateral bonds, opening it up into an acyclic cation after a cascade of rearrangements, initiated by vibronic coupling.

mall ring propellanes form a family of cage compounds that display many intriguing features. The smallest member of the family, [1.1.1]propellane (1), is quite stable, both kinetically and thermodynamically, despite its high strain energy 1. With its pair of bridgehead carbon atoms in an inverted tetrahedron topology (Fig. 1), it possesses a rather unusual structure. Although such a molecular shape would suggest that it is a diradical, its closed-shell character is well established2 and several clues point to the existence of a central bond (shown in red) despite the inverted configuration: a short central CC distance (0.20 shorter than in the diradical triplet state), and thermodynamic estimations that are compatible with a central bond strength of approximately 60 kcal mol1 (ref. 2). A negative orbital overlap population, however, combined with an inconclusive electron density map in the inter-bridgehead region1, have cast some doubt about the existence of this central bond. The issue has been investigated theoretically, resulting in suggestions that a central CC bond does indeed exist, but not of the usual covalent type3,4. Furthermore, a valence bond study also found the existence of a non-classical central CC bond a charge-shift bond in which the resonance energy between covalent and ionic forms plays a major role5. On top of all these mysteries around [1.1.1]propellane, writing in the Journal of the American Chemical Society, Thomas Bally, Ffrancon Williams and co-workers
96

H2 C C CH2

-eH2C

~ ~
C

H2 C C CH2 H2C

CH2 C C CH2

CH2 C C CH2

CH2 C C CH2

...

C H2C

H2C

H2C

1+ 3+
H2 C CH2 C CH2 H2C C C H2 C C H2C

CH2 C C

C H2C

~ ~

~ ~

C CH2 H2C

CH2

CH2

5+ -e-

2+

4+

Figure 1 | Oxidation of [1.1.1]propellane 1, leading to a primary radical cation 1+, which further rearranges to 3+ through a three-step process. The green-coloured bonds are those that are broken in the process; the wavy lines indicate those that will be broken in the next step. Oxidation of dimethylenecyclopropane 2 also leads to 3+, which cyclizes to 4+ under near-infrared photolysis. Red indicates the central bond.

now reveal6 that the corresponding cation is as fascinating as its neutral counterpart. Prior to this joint experimental and theoretical study it was thought, on the basis of converging arguments, that 1 kept its geometrical cage shape under oneelectron oxidation. The highest occupied molecular orbital (HOMO) of 1 is totally symmetric and clearly non-bonding, therefore extracting an electron from it was not expected to lead to significant structural changes. Accordingly, analysis of the photoelectron spectrum of 1 only showed very small geometry changes on ionization7.

This was also in good agreement with an earlier ab initio calculation, which predicted the cage-like cation (1+ in Fig. 1) to be a stationary point on the potential surface2. Bally, Williams and co-workers, however, show 6 that the electron spin resonance (ESR), infrared (IR) and optical spectra of the ionized molecule are incompatible with a species having the structure and the high symmetry of 1. For example, the ESR spectrum features a set of four and a set of two equivalent hydrogen atoms rather than a unique set of six, as the cage 1+ would imply. The actual structure of the cation of

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