Insertion of CO 2 into the carbon – boron bond of a boronic ester ligand †

Discovery of new fundamental reactivity of CO2 is of interest because it may lead to new ways to sequester CO2 and utilize CO2 as a C1 feedstock for synthesis. 1 Known reactivity of CO2 includes coordination to metal centres, insertion into M–X bonds (where M is a metal center and X is an element, most commonly H or C) and adduct formation with a Lewis base (with or without the assistance of a Lewis acid). These fundamental reactivities have resulted in the catalytic conversion of CO2 into a variety of reduced products, which is a topic that has been reviewed and has seen a flurry of recent progress. Our group has demonstrated formal insertion of CO2 into the C–H bond of an actor diazafluorenyl (L ) ligand supported by a spectator metal center. We elaborated this work to include metal-free insertions, and catalytic hydroboration of CO2. Although we have not yet studied the catalytic mechanism in detail, one plausible pathway involves borylation of the diazafluorenyl moiety and subsequent insertion of CO2 into the newly formed C–B bond. To our knowledge, the direct insertion of CO2 into a C–B bond is unknown prior to this work, and represents a new mode of reactivity for the thermodynamically stable CO2 molecule. Related yet distinct C–B bond reactivity was reported by Shoji et al. who employed salts containing the electrophilic Mes2B + in a deoxygenation-arylation of CO2. 34 In this reaction, one mesityl group is transferred to the carbon of CO2, generating MesCQO. Piers et al. recently activated CO2 in ring expansion reactions using the reactive C–B bonds of isomeric doubly reduced diborole and bis-cycloborabutylidene derivatives.‡ Two examples of related insertions of CO2 have also recently emerged: Waterman et al. observed an unexpected insertion of CO2 into reactive C–Si bonds in Zn complexes chelated by a pair of 2-(phosphinomethyl)pyridine ligands, and Knopf and Cummins demonstrated formal insertion of CO2 into three B–H bonds in borohydride salts to form [HB(OCHO)3] . Herein we report the reactivity of [Ru(CO)(H)L(PPh3)2], 1a and [ZnL(Mes2nacnac)], 1b toward pinacolborane (HBpin) to generate the corresponding complexes 2a and 2b of an actor diazafluorenylboronic ester ligand. This actor ligand inserts CO2 into its C–B bond, which is an unprecedented mode of reactivity for the boronic ester functional group. We also report the catalytic activities of these complexes towards CO2 reduction with catecholborane (HBcat) and HBpin. As shown in Scheme 1, 1a was synthesized in 59% yield from the reaction of NaL and [RuHCl(CO)(PPh3)3]. The spectroscopic properties of 1a are similar to those of [Ru(H)L(N2)(PPh3)2] (n(N2) = 2092 cm ), except that its characteristic infrared absorption occurs at 1918 cm 1 due to stretching of the CO ligand.

Discovery of new fundamental reactivity of CO 2 is of interest because it may lead to new ways to sequester CO 2 and utilize CO 2 as a C 1 feedstock for synthesis. 1Known reactivity of CO 2 includes coordination to metal centres, 2 insertion into M-X bonds (where M is a metal center and X is an element, most commonly H or C) [3][4][5] and adduct formation with a Lewis base (with or without the assistance of a Lewis acid). 6,73][14][15][16][17][18][19][20][21][22][23][24][25][26][27][28][29][30][31] Our group has demonstrated formal insertion of CO 2 into the C-H bond of an actor diazafluorenyl (L À ) ligand supported by a spectator metal center. 32We elaborated this work to include metal-free insertions, 33 and catalytic hydroboration 28 36 and Knopf and Cummins demonstrated formal insertion of CO 2 into three B-H bonds in borohydride salts to form [HB(OCHO) 3 ] À . 37erein we report the reactivity of [Ru(CO)(H)L(PPh 3 ) 2 ], 1a and [ZnL(Mes 2 nacnac)], 1b toward pinacolborane (HBpin) to generate the corresponding complexes 2a and 2b of an actor diazafluorenylboronic ester ligand.This actor ligand inserts CO 2 into its C-B bond, which is an unprecedented mode of reactivity for the boronic ester functional group.We also report the catalytic activities of these complexes towards CO 2 reduction with catecholborane (HBcat) and HBpin.
As shown in Scheme 1, 1a was synthesized in 59% yield from the reaction of NaL and [RuHCl(CO)(PPh 3 ) 3 ].The spectroscopic properties of 1a are similar to those of [Ru(H)L(N 2 )(PPh 3 ) 2 ] (n(N 2 ) = 2092 cm À1 ), 38 except that its characteristic infrared absorption occurs at 1918 cm À1 due to stretching of the CO ligand.
1b was synthesized by protonolysis in two steps from diethylzinc with an overall 87% yield.In the 1 H NMR spectrum of 1b one resonance exists for each pair of pyridyl protons, which are related to each other through a mirror plane of symmetry.Protons on nacnac are similarly related, consistent with C 2v symmetry in solution.The solid state structure of 1b (see ESI †) features a ZnN 4 core with distorted tetrahedral geometry.
With 1a and 1b in hand, we investigated the stoichiometric reactivity of the diazafluorenyl complexes towards HBpin: when a toluene solution of complex 1a is heated with HBpin, 2a is formed with concomitant formation of H 2 (Scheme 2).Presumably the formation of 2a starts with the formation of an adduct between the carbanion of 1a and HBpin.This interaction brings B-H and C-H bonds into close proximity, which allows the loss of H 2 .In the transformation from 1a to 2a the diazafluorenyl ligand acts and the Ru centre spectates.
The borylation of 1a brings about a change in the carbonyl stretching frequency from 1918 cm À1 in the starting material to 1936 cm À1 in the product.The higher C-O bond strength in 2a indicates the electron-withdrawing nature of the newly formed diazafluorenylboronic ester ligand relative to the parent L À ligand in 1a.In C 6 D 6 at ambient temperature, complex 2a displays a singlet at 48.47 ppm in its 31 P{ 1 H} NMR spectrum; the hydride resonates at À11.68 ppm as a triplet ( 2 J P-H = 20 Hz) and the diazafluorenyl moiety shows one signal for each of its six protons in its 1 H NMR spectrum.
As shown in Fig. 1, the solid state structure of 2a has been confirmed with X-ray crystallography.The structure of 2a features a pseudo-octahedral Ru centre with two mutually trans phosphine ligands and the hydride and carbonyl ligands oriented in a cis fashion.The diazafluorenylboronic ester ligand chelates the Ru centre through its two nitrogen donor atoms.The Ru1-N1 bond length of 2.171(2) is shorter than the Ru1-N2 bond length of 2.266(2) due to the greater trans influence of the hydride ligand relative to CO.The sum of the bond angles around C5 is 359.9(5)1 which suggests sp 2 hybridization.The B atom is three-coordinate and the O2-B1-O3 group is nearly coplanar with diazafluorenyl (a dihedral angle of 61) such that p-donation of the carbanion into the vacant p orbital on B is possible.The C5-B1 bond length is 1.512(4) Å, which is similar to pinacol esters of other borylated cyclopentadienyl (Cp) compounds (12-crown-4)LiCpBpin (1.488(8) Å) and (Cp 2 Ru)Bpin (1.537(12) Å). 39,40 In such compounds the boratafulvene resonance form also contributes to the bonding picture, having C-B bond lengths between a typical C(sp 2 )-B(sp 2 ) single bond (e.g., 1.58 Å in BMes 3 ) 41 and a formal C(sp 2 )-B(sp 2 ) double bond (e.g., 1.444(8) Å in simple borataalkene [Mes 2 BQCH 2 ] À ). 42milarly, when 1b was heated in THF in the presence of HBpin an analogous borylation of diazafluorenyl occurred and 2b formed.Similar to 1b, the NMR data for 2b reveal a symmetric structure in solution.2b crystallizes from toluene/pentane with two molecules in the asymmetric unit (see ESI †).The distorted tetrahedral ZnN 4 core persists; the metric parameters around Zn are similar to those in 1b, and the metric parameters of the diazafluorenylboronic ester ligand are similar to those in 2a.
With 2a and 2b in hand we set about investigating their reactivity towards CO 2 .When CO 2 is introduced to a solution of 2a in toluene-diethylether (1 : 1 v/v), the colour of the solution changes from pink to orange (Scheme 2).The formation of 3a can be confirmed by NMR experiments, in which all the 1 H signals have shifted slightly compared to those of 2a and an additional 13 C signal appears at 162.29 ppm corresponding to the newly formed ester group from CO 2 .In the infrared spectrum of 3a, the ester carbonyl stretch appears at 1647 cm À1 , and the CO ligand stretch is shifted to 1942 cm À1 .X-ray crystallography confirmed the structure of 3a as shown in Fig. 1.Diazafluorenyl is nearly coplanar with its appended carboxylate group, and the B atom is canted out of this plane, giving an O2-C51-O3-B1 dihedral angle of B371.When CO 2 is introduced to a C 6 D 5 Br solution of 2b, a similar change in colour and in spectral data occurs as the boryl ester product 3b forms; we confirmed the structure by X-ray crystallography (see ESI †).
The insertion of CO 2 into the C-B bond of 2a and 2b is intriguing from the standpoint of providing a new type of reactivity for the thermodynamically stable and environmentally deleterious CO 2 molecule.To understand this transformation further, DFT calculations have been used to locate the transition state of the insertion reaction from 2a to 3a and to obtain the thermodynamic data (see ESI † for details).The transition state of the insertion features a C-C-O-B four-membered ring (Fig. 2  examine the possibility of a two-step mechanism for the insertion reaction, i.e., C-C bond formation first, followed by the migration of the Bpin moiety.All attempts to locate the C-C formation intermediate failed.Although it is still possible that such an intermediate may sit in an extremely shallow well, our computation is consistent with the one-step CO 2 insertion mechanism.The DH of the overall reaction is À15.9 kcal mol À1 , while the DH a is 13.1 kcal mol À1 , so it is unsurprising that the insertion reaction occurs readily at ambient temperature.
This unique reactivity led us to investigate whether borylester 3a is sufficiently reactive towards further reduction of the CO 2 -derived moiety.Heating a C 6 D 6 solution of 3a to 110 1C in the presence of 20 equivalents of HBpin led to a 0.9 : 1 ratio of 2a : 3a in 8 hours as detected by 1 H NMR spectroscopy, accompanied by the formation of CH 3 OBpin and pinBOBpin.This reactivity represents the closing of a synthetic loop: the reactive diazafluorenylboronic ester 2a inserts CO 2 to make boryl ester 3a, which upon reaction with HBpin regenerates 2a and liberates the product of CO 2 reduction.
With the synthetic loop established, we tested the performance of complexes 1 and 2 in catalytic hydroboration of CO 2 with HBcat and HBpin (Table 1).1a and 1b perform similarly as catalysts: their average turnover frequencies (avg.TOF) are on the order of one per hour, and the methoxyborane derivative CH 3 OBR 2 was the major CO 2 reduction product in all cases.In the hydroboration of CO 2 with HBcat, 1a and 1b are not as active as (N-methyl)diazafluorenide (avg.TOF = 16 h À1 at 25 1C).However, when HBpin is used as the reductant, 1a and 1b are capable of more turnovers compared to (N-methyl)diazafluorenide (avg.TOF = 0.28 at 100 1C in CDCl 3 ). 28Interestingly, 2a and 2b showed comparable catalytic performance for CO 2 hydroboration with HBpin under the same respective conditions compared to the parent compounds 1a and 1b (Table 1).In the Ru case the borylated species led to a slight increase in total TON (from 39 to 60).In the Zn case the borylated version led to a slight decrease in total TON (from 48 to 40).Unfortunately, we could not identify any metal containing species from the catalytic reaction mixtures.Therefore, the relevance of the steps in the synthetic loop to the actual catalytic runs has yet to be determined through further mechanistic studies.
In summary, new compounds 1a and 1b undergo C-H bond borylation to yield diazafluorenylboronic ester complexes 2a and 2b, which feature the unquenched p-basicity of a carbanionic group directly bound to a boron centre.It is this structural feature that facilitates the unprecedented insertion of CO 2 into their C-B bonds to yield boryl ester products 3a and 3b.DFT calculations suggest the insertion occurs in a concerted fashion.Compound 3a can be converted to 2a when reacted with HBpin, releasing the CO 2 reduction product CH 3 OBpin and closing a synthetic loop of CO 2 reduction.Furthermore, compounds 1 and 2 all displayed catalytic activity toward CO 2 hydroboration with HBpin and HBcat.Further mechanistic studies of the catalytic CO 2 reduction, the insertion of other unsaturated substrates into the C-B bond in our diazafluorenylboronic ester ligand, the related reactivities of other C-E bonds, and the corresponding catalytic reactions are under investigation in our laboratory.
We thank NSERC of Canada for funding.T. J. and Y. Y. thank the government of Ontario for OGS and Trillium scholarships, respectively.A. P. and E. Y. thank NSERC for respective CGS-M and USRA awards.We also acknowledge the CFI Project #19119, and the Ontario Research Fund for funding the CSICOMP NMR lab at the University of Toronto enabling the purchase of several new spectrometers.Notes and References ‡ The authors posit that CO 2 catalyzes the rearrangement of the biscycloborabutylidene into the diborole, which reacts with CO 2 in a pair of ring expansions from five to six members, distinct from from simple insertion into the reactive C-B bonds.
of CO 2 .Although we have not yet studied the catalytic mechanism in detail, one plausible pathway involves borylation of the diazafluorenyl moiety and subsequent insertion of CO 2 into the newly formed C-B bond.To our knowledge, the direct insertion of CO 2 into a C-B bond is unknown prior to this work, and represents a new mode of reactivity for the thermodynamically stable CO 2 molecule.Related yet distinct C-B bond reactivity was reported by Shoji et al. who employed salts containing the electrophilic Mes 2 B + in a deoxygenation-arylation of CO 2 . 34In this reaction, one mesityl group is transferred to the carbon of CO 2 , generating MesCQO + .Piers et al. recently activated CO 2 in ring expansion reactions using the reactive C-B bonds of isomeric doubly reduced diborole and bis-cycloborabutylidene derivatives.‡ 35 Two examples of related insertions of CO 2 have also recently emerged: Waterman et al. observed an unexpected insertion of CO 2 into reactive C-Si bonds in Zn complexes chelated by a pair of 2-(phosphinomethyl)pyridine ligands, Scheme 2 Borylation and carboxylation of diazafluorenyl complexes.

Fig. 1
Fig. 1 Molecular structures of 2a and 3a.Ellipsoids are shown at 30% probability.Hydrogen atoms except for hydrides omitted for clarity.Only one disordered component is shown.Co-crystallized molecules are removed for clarity.

Fig. 2
Fig. 2 Computed transition state structure of the CO 2 insertion reaction from 2a to 3a Colour key: O, red; N, blue; P, orange; B, green; Ru, pink; C, gray; H, white.

Table 1
Results for the catalytic hydroboration of CO 2 by HBcat and HBpin a