The synthesis of a new iridium(I) complex containing an enamido phosphine anion (dbuP(-)) and its unique reactivity with CO2 is reported. The complex binds two equivalents of CO2 and initiates a highly selective reaction cascade. The reaction leads to the reversible cleavage of CO2 and the enamido ligand as well. Computational analysis points to the existence of a relatively stable Ir-CO2 complex as a reaction intermediate prior to CO2 cleavage, which was confirmed experimentally. The observed transformation resembles several aspects of enzymatic CO2 fixation by RuBisCO

Anderson

Andersson

Appel

Aresta

Bianchini

Braunstein

Cokoja

Dobrovetsky

Feller

García-España

González-Sebastián

Herskovitz

Ho Shin

Huff

Janes

Knowles

Langer

McDonald

McGrew

O'Reilly

Ohnishi

Rivada-Wheelaghan

Ruben

Taylor

Truscott

van Bochove

Vogt

Waldrop

Langer, Jens

Hamza, Andrea

Pápai, Imre

Repository of the Academy's Library

COMMUNICATION              RuBisCO-inspired CO2 Activation and Transformation by an Iridium(I) Complex Jens Langer,*[a] Andrea Hamza,[b] and Imre Pápai*[b]  Abstract: Synthesis of a new iridium(I) complex comprising an enamido phosphine anion dbuP‒ and its unique reactivity with CO2 is reported. The complex binds two equivalents of CO2 and initiates a highly selective reaction cascade. The reaction leads to the reversible cleavage of CO2 and the enamido ligand as well. Computational analysis points to the existence of a relatively stable Ir-CO2 complex as reaction intermediate prior to CO2 cleavage, which could be confirmed experimentally. The observed transformation resembles several aspects of the enzymatic CO2 fixation by RuBisCO. The development of novel reaction cascades for the fixation of CO2, its transformation and incorporation in organic matter remains a major challenge for synthetic chemists.[1] Inspiration for the design of new metal complexes for CO2 capture can be found in biological systems, where CO2 fixation via C-C linkage is mediated by biotin dependent enzymes [2] or catalyzed by ribulose-bisphosphate carboxylase/oxygenase (RuBisCO).[3] The latter acts as a catalyst for the direct carboxylation of ribulose-bisphosphate (RuBP) at the C2 carbon and its subsequent cleavage to form 3-phosphoglycerate (3-PGA) in the Calvin cycle, which is the essential step for the biosynthesis of carbohydrates from atmospheric CO2 (see Fig. 1a). Despite RuBisCO’s ubiquitous presence in plants, which makes it one of the most abundant enzymes on earth, small molecule model compounds of this enzyme are scarce. Nevertheless, the CO2 fixation by RuBisCO features some interesting aspects, which could facilitate CO2 transformation by other metal complexes as well, if they could be adopted. One of the key features is the cooperative uptake of two CO2 molecules by the enzyme with different functions and fate. The first CO2 is required for enzyme activation, which takes place by carbamate formation at a lysine residue and subsequent capture of a Mg2+ ion,[4] while only the second CO2 is used for carboxylation of the substrate (see Fig. 1b). Surprisingly, attempts to design RuBisCO-inspired model compounds with Mg2+ [5] and other metal ions[6] focused on the carbamate formation step, although the C-C bond formation between the second CO2 and the   Figure 1. CO2 fixation by RuBisCO. a) Reaction cascade observed in the enzymatic carboxylation of ribulose-bisphosphate (RuBP) by RuBisCO; b) Schematic representation of the active center during enzyme activation, substrate binding and carboxylation (▬ protein backbone, amino acid sequence numbers correspond to spinach RuBisCO). substrate RuBP in its endiolate form is the key function of the enzyme. This makes enolates or related substance classes such as enamides promising substrates in small molecular systems, which aim for C-C bond formation rather than carbamylation.[7] While magnesium is nature's metal of choice in this essential enzyme, this selection seems markedly influenced by the abundance of the Mg2+ ion. When thinking about synthetic metal complexes, being able to incorporate two CO2 molecules in analogy to the natural ideal, but without the help of a protein shell as highly sophisticated multifunctional ligand, other metal ions appear better suited. For instance, the combination of enolato or enamido ligands as model substrates with a low-valent CO2-affine metal center (e.g. IrI)[8] might be suitable. Along these lines, we synthesized new IrI complexes comprising a chelating enamido phosphine anion dbuP‒ [9] (see Fig. 2a). This enamido derivative is easily accessible by deprotonation of the dbu-modified phosphine 6-diphenyl-phosphanyl-1,8-  [a] Dr. J. Langer Inorganic and Organometallic Chemistry Friedrich-Alexander University Erlangen-Nürnberg Egerlandstraße 1, 91058 Erlangen, Germany E-mail: jens.langer@fau.de [b] Dr. A. Hamza, Dr. I. Pápai  Research Centre for Natural Sciences,  Hungarian Academy of Sciences,  Magyar tudósok körútja 2, H-1117 Budapest, Hungary E-mail: papai.imre@ttk.mta.hu  Electronic Supporting information (ESI) for this article is given via a link at the end of the document. COMMUNICATION                   Figure 2. a) Synthesis of 1 and 2; b) Reversible CO2 fixation by 2a. c) ORTEP plots of 2a (left) and 3 (right), ellipsoids drawn at 50% probability level, H atoms omitted for clarity. diazabicyclo[5.4.0]undec-7-ene (dbuPH),[10] and its phosphine moiety ensures tight bonding to Ir centers. Salt metathesis with a lithium compound provided access to [Ir(cod)(dbuP)] (1) (see Fig. 2a and ESI), which, however, showed no reactivity towards CO2 at ambient temperature. Neither carbamate formation nor carboxylation at the carbon atoms of the enamido moiety was detected, which contrasts recent investigations on related RuII, ReI, FeII, and IrIII systems.[8e,11] This is not surprising, since 1 lacks an electrophilic metal center, which promotes CO2 fixation via M-O bond formation occurring simultaneously with the carboxylation of the enamide. Instead, the low-valent IrI center in 1 is rather basic, yet not enough to capture CO2 by a nucleophilic attack.  In order to investigate the potential of two different adjacent nucleophilic sites in CO2 capture, we then increased the metal basicity by exchanging the cod ligand in 1 by the basic 1,2-bis(diethylphosphino)ethane (depe), thus enhancing the affinity  Figure 3. Temperature-dependent re-formation of 2a from 3 in C6D6, monitored by 31P{1H} NMR spectroscopy (middle and bottom); spectrum of 2a for comparison (top). of the metal center towards CO2. The resulting product [Ir(depe)(dbuP)] (2a) can be isolated as red crystals in 72% yield (see Fig. 2c). In contrast to 1, compound 2a reacts readily and highly selectively with two equivalents of CO2. A single product 3 was formed within seconds, when a solution of 2a was exposed to a CO2 atmosphere at ambient temperature. The CO2 uptake is related to an increase of the molecular mass of the species by m/z = 88 to m/z = 823.25 (M+1; by ESI-mass spectrometry), as expected for the incorporation of two equivalents of CO2. 13C NMR spectroscopy revealed signals at 163.4 and 174.4 ppm, which correspond to the carbon atoms of former CO2 molecules. A coupling of two CO2 at the IrI center, which earlier led to the iridacycles [(Me2RP)3P)3Ir(Cl){C(O)OC(O)O}] (R = Me, Ph)[8a,d] and [(tBu-PNP)Ir(H){C(O)OC(O)O})][8e] (tBu-PNP = 2,6-bis(tBu2PCH2)2-pyridine), can be ruled out by IR spectroscopy, since a strong resonance at 2024 cm-1 indicates the presence of a CO ligand. XRD analysis confirmed the CO ligand and allowed unambiguous identification of the product as [Ir(depe)(CO)(Ph2PO)(dbuCO2)] (3) (see Fig. 2b). In analogy to the RuBisCO mediated reaction, the model substrate dbuP‒ was C-carboxylated and split into two parts upon the reaction cascade. Formally, the Ph2P+ subunit of dbuP‒ was replaced by CO2, leading to the novel dianionic ligand [dbuCO2]2‒. The splitting of the substrate is accompanied by a two-electron oxidation of Ir and the reduction of a second CO2 to CO, while the remaining oxygen atom recombines with the P-containing substrate fragment to the phosphinite [Ph2PO]‒. Given the nature of 3, it is astonishing that its formation, which is achieved by the formation of 4 different new bonds (Ir-C, Ir-O, C-C, P-O) and the rupture of two others (C=O, P-C), is reversible. When a solution of 3 in C6D6 was placed under a N2 atmosphere and heated to 70 °C, the dbuP‒ moiety reassembled and the formation of [Ir(depe)(dbuP)] (2a) was clearly detected by NMR methods (see Fig. 3). DFT calculations on the reaction mechanism (see Fig.4 and ESI) reveal that the first CO2 binds preferentially to the enamide moiety of the dbuP ligand leading to a C-carboxylated ligand [dbuPCO2]‒ in intermediate I1. This species is predicted to be only 2.9 kcal/mol above the reactant state in free energy and the barrier of this C-C bond formation process is 15.7 kcal/mol. An alternative pathway corresponding to η1C-type coordination of CO2 to the Ir center gives a significantly less stable species I1' COMMUNICATION              (G = 10.5 kcal/mol; see Fig. 4b). Interestingly, the fixation of the second CO2 is found to be thermodynamically favored with respect to both I1 and I1' species, pointing to a high degree of cooperativity in the CO2 uptake. The structure of intermediate I2 illustrates that unlike in I1, the carboxylate group coordinates to Ir, and the Ir-C bond of the η1C-coordinated CO2 is strengthened, when compared to that in I1'. These structural changes indeed confirm the beneficial interplay between the two CO2 molecules. The cooperative mechanism operates via the metal center, which acts simultaneously as a Lewis acid (interaction with the carboxylate) and a Lewis base (coordination of CO2) (see ESI). Due to IrCO2 charge transfer, the O atoms of the coordinated CO2 in I2 become more nucleophilic, which initiates a nucleophilic substitution at the neighboring Ph2P group (SN2@P  mechanism).[12] In this transformation, the dianion [dbuCO2]2- is the leaving group, which remains attached to the metal via Ir-N and Ir-O bonds (see I3, Fig. 4c). The related transition state TS3 describes a concerted P-O bond formation and P-C bond cleavage event, and it represents the rate determining step of the reaction cascade. The overall barrier is thus predicted to be 21.9 kcal/mol, which is consistent with the observed reaction rate. The energetically high-lying intermediate I3 (G = 16.5 kcal/mol) involves a strained four membered IrCOP ring, which can easily open via transition state TS4 to yield the CO ligand and the [Ph2PO]‒ anion in product 3.[13] The calculations indicate that the Ir-O bond formed with the carboxylate moiety is gradually strengthened upon the I2I33 transformation suggesting that in addition to cooperative CO2 binding, this functionality also has an important role in the substrate cleavage phase of the reaction. The Gibbs free energy of the overall transformation 2a + 2CO2  3 is predicted to be close to zero (G = -0.3 kcal/mol), in good agreement with the observed reversibility of the reaction.  The plausibility of the computationally revealed reaction mechanism was probed experimentally. Given that the transformation of I2 to I3 is the rate determining step, trapping of I2 at low temperature seemed feasible. Indeed, when a solution of 2a in toluene-d8 was exposed to a 13CO2 atmosphere at 203 K, a single species [Ir(depe)(CO2)(dbuPCO2)], incorporating two equivalents of 13CO2 was formed. In the 13C NMR spectrum signals at δC = 171.1 and 142.0 ppm are indicative for the formed carboxylate moiety and the η1C-coordinated CO2 ligand, respectively, as in I2. Upon warm-up, transformation of this CO2 complex to compound 3 sets in at ≈220 K without detectable intermediates.  It is noteworthy that the high metal basicity in 2a plays a crucial role in the observed transformation. Lowering the basicity, either by the exchange of depe for a less basic phosphine (e.g. dppe) or by use of a less basic metal (e.g. Rh) renders the resulting complexes [Ir(dppe)(dbuP)] (2b) (see Fig. 2) and [Rh(depe)(dbuP)] (4) (see ESI) inactive. Just as 2a, these two derivatives are still competent to bind two eq. of CO2 at 203 K (see ESI), although with increasing difficulty (CO2 affinity 2b<4<2a), but a transformation into products of the type of 3 is not observed.  In conclusion, we developed a simple iridium system, which is capable to reversible activate and incorporate two equivalents of CO2 by a cascade process that involves the formation and cleavage of 6 different bonds in a highly selective manner.  Figure 4. a) Free energy profile for the 2a + 2CO2 → 3 reaction. Computationally identified intermediates and transition states for b) cooperative CO2 binding and c) dbuP‒ and CO2 cleavage. Selected bond distances are given in Å. All H atoms, Ph groups of dbuP‒ and Et groups of depe are omitted for clarity. Bonds formed or cleaved in transition states are highlighted by red dashed lines. Relative stabilities (in kcal/mol; relative to 2a + 2CO2) are given in parentheses. Cooperative CO2 binding by two adjacent nucleophilic sites within the metal complex was exploited to generate a system that shows remarkable similarities to RuBisCO. Both systems share the requirement of two CO2 molecules to be functional, a common substrate class as well as the C-carboxylation and splitting of the substrate, although by different mechanisms. These findings may launch new strategies for activation and transformation of unreactive substrates such as CO2.  -5.00.05.010.015.020.025.0G(kcal/mol)a)2a + 2CO2I1 + CO2 (2.9)TS1 (15.7)I3 (16.5)3 (-0.3)TS2 (14.9)TS3 (21.9)TS4 (18.1)I2 (1.9)cooperative CO2 fixation dbuP− and CO2 cleavageb)c)2.152.092.432aI2 (1.9)I1’ (10.5)+ CO2+ CO2+ CO2+ CO23.60I1 (2.9)2.061.87I23 (-0.3)1.762.132.581.902.062.101.661.46I3 (16.5)TS3 (21.9) TS4 (18.1)COMMUNICATION              Acknowledgements We are grateful for the financial support of project LA2474/3-1 by the Deutsche Forschungsgemeinschaft (DFG). We thank Prof. I. Ivanović-Burmazović for access to the UHR-TOF Bruker Daltonik maXis 5G mass spectrometer and M. Dürr for the corresponding measurements, and Dr. C. Färber and J. Schmidt for the low temperature NMR measurements. A. H. acknow-ledges the János Bolyai Scholarship from the Hungarian Academy of Sciences. Computer facilities provided by NIIF HPC Hungary is also acknowledged. Keywords: Iridium • carbon dioxide • RuBisCO • C-C bond formation • metal basicity [1] For recent reviews see: a) M. Cokoja, C. Bruckmeier, B. Rieger, W. A. Herrmann, F. E. Kühn, Angew. Chem. Int. Ed. 2011, 50, 8510; b) A. M. Appel, J. E. Bercaw, A. B. Bocarsly, H. Dobbek, D. L. DuBois, M. Dupuis, J. G. Ferry, E. Fujita, R. Hille, P. J. A. Kenis, C. A. Kerfeld, R. H. Morris, C. H. F. Peden, A. R. Portis, S. W. Ragsdale, T. B. Rauchfuss, J. N. H. Reek, L. C. Seefeldt, R. K. Thauer, G. L. Waldrop, Chem. Rev. 2013, 113, 6621; c) M. Aresta, A. Dibenedetto, A. Angelini, Chem. Rev. 2014, 114, 1709−1742; d) T. Janes, Y. Yang, D. Song, Chem. Commun. 2017, 53, 11390. [2] a) J. R. Knowles, Annu. Rev. Biochem. 1989, 58, 195-221; b) G. L. Waldrop, H. M. Holden, M. St. Maurice, Protein Sci. 2012, 21, 1597. [3] I. Andersson, A. Backlund, Plant. Physiol. Bioch. 2008, 46, 275. [4] T. C. Taylor, I. Andersson, Nat. Struct. Biol. 1996, 3, 95. [5] a) M. Ruben, D. Walther, R. Knake, H. Görls, R. Beckert, Eur. J. Inorg. Chem. 2000, 1055; b) T. M. McDonald, J. A. Mason, X. Kong, E. D. Bloch, D. Gygi, A. Dani, V. Crocella, F. Giordanino, S. O. Odoh, W. S. Drisdell, B. Vlaisavljevich, A. L. Dzubak, R. Poloni, S. K. Schnell, N. Planas, K. Lee, T. Pascal, L. F.Wan, D. Prendergast, J. B. Neaton, B. Smit, J. B. Kortright, L. Gagliardi, S. Bordiga, J. A. Reimer, J. R. Long, Nature 2015, 519, 303. [6] E. García-España, P. Gaviña, J. Latorre, C. Soriano, B. Verdejo, J. Am. Chem. Soc. 2004, 126, 5082. [7] a) P. Braunstein, D. Matt, Y. Dusausoy, J. Fischer, A. Mitschler, L. Ricard, J. Am. Chem. Soc. 1981, 103, 5115; b) G. I. McGrew, P. A. Khatri, W. E. Geiger, R. A. Kemp, R. Waterman, Chem. Commun. 2015, 51, 15804. [8] a) T. Herskovitz, L. J. Guggenberger, J. Am. Chem. Soc. 1976, 98, 1615–1616; b) T. Herskovitz, J. Am. Chem. Soc. 1977, 99, 2391; c) D. W. Lee, C. M. Jensen, D. Morales-Morales, Organometallics 2003, 22, 4744; d) J. Langer, W. Imhof, M. J. Fabra, P. García-Orduña, H. Görls, F. J. Lahoz, L. A. Oro, M. Westerhausen, Organometallics 2010, 29, 1642; e) M. Feller, U. Gellrich, A. Anaby, Y. Diskin-Posner, D. Milstein, J. Am. Chem. Soc. 2016, 138, 6445. [9] a) J. Langer, B. Maitland, S. Grams, A. Ciucka, J. Pahl, H. Elsen, S. Harder, Angew. Chem. Int. Ed. 2017, 56, 5021; b) J. Langer, S. Grams, R. Puchta, Eur. J. Inorg. Chem. 2017, 2671. [10] M. O'Reilly, R. Pattacini, P. Braunstein, Dalton Trans. 2009, 6092. [11] a) C. A. Huff, J. W. Kampf, M. S. Sanford, Organometallics 2012, 31, 4643; b) M. Vogt, A. Nerush, Y. Diskin-Posner, Y. Ben-David, D. Milstein, Chem. Sci. 2014, 5, 2043; c) O. Rivada-Wheelaghan, A. Dauth, G. Leitus, Y. Diskin-Posner, D. Milstein, Inorg. Chem. 2015, 54, 4526. [12] M. A. van Bochove, M. Swart, F. M. Bickelhaupt, J. Am. Chem. Soc. 2006, 128, 10738-10744. [13] For related examples of O transfer from CO2 to phosphines see: a) C. Bianchini, C. Mealli, A. Meli, M. Sabat, Inorg. Chem. 1984, 23, 2731; b) J. Ho Shin, D. G. Churchill, G. Parkin, J. Organomet. Chem. 2002, 642, 9; c) T. Ohnishi, H. Seino, M. Hidai, Y. Mizobe, J. Organomet. Chem. 2005, 690, 1140; d) J. S. Anderson, V. M. Iluc, G. L Hillhouse, Inorg. Chem. 2010, 49, 10203; e) L. González-Sebastián, M. Flores-Alamo, J. J. García, Dalton Trans. 2011, 40, 9116; f) R. Dobrovetsky, D. W. Stephan, Angew. Chem. Int. Ed. 2013, 52, 2516. COMMUNICATION               Entry for the Table of Contents (Please choose one layout)  Layout 1:  COMMUNICATION CO2perative effort. The highly selective binding and transformation of CO2 by an iridium complex clearly shows cooperative effects between the two CO2 molecules involved. The reversible transformation resembles some aspects of the CO2 binding by the RuBisCO enzyme.    Jens Langer,*[a] Andrea Hamza,[b] and Imre Pápai* Page No. – Page No. RuBisCO-inspired CO2 Activation and Transformation by an Iridium(I) Complex      Layout 2:  COMMUNICATION Text for Table of Contents  Author(s), Corresponding Author(s)* Page No. – Page No. Title      ((Insert TOC Graphic here)) 

RuBisCO-Inspired CO2 Activation and Transformation by an Iridium(I) Complex

Jens Langer

Andrea Hamza

Imre Pápai

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RuBisCO-Inspired CO<sub>2</sub>
 Activation and Transformation by an Iridium(I) Complex

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RuBisCO-Inspired CO2 Activation and Transformation by an Iridium(I) Complex

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