Heather
Fish
,
Sam
Hart
,
Katie J.
Lamb
,
Michael
North
*,
Sophie C. Z.
Quek
,
Adrian C.
Whitwood
,
Barnaby
Woods
and
Xiao
Wu
Department of Chemistry, University of York, Heslington, York YO10 5DD, UK. E-mail: michael.north@york.ac.uk
First published on 15th December 2020
The crystal structure of [Al(tBu-salen)]2O·HCl shows major changes compared to that of [Al(tBu-salen)]2O. The additional proton is localized on the bridging oxygen atom, making the aluminium atoms more electron deficient. As a result, a water molecule coordinates to one of the aluminium atoms, which becomes six-coordinate. This pushes the salen ligand associated with the six-coordinate aluminium ion closer to the other salen ligand and results in the geometry around the five-coordinate aluminium atom becoming more trigonal bipyramidal. These results experimentally mirror the predications of DFT calculations on the interaction of [Al(tBu-salen)]2O and related complexes with carbon dioxide. Variable temperature NMR studies of protonated [Al(tBu-salen)]2O complexes revealed that the structures were dynamic and could be explained on the basis of an intramolecular rearrangement in which the non-salen substituent of a five-coordinate aluminium(tBu-salen) unit migrates from one face of a square based pyramidal structure to the other via the formation of structures with trigonal bipyramidal geometries. Protonated [Al(tBu-salen)]2O complexes were shown to have enhanced Lewis acidity relative to [Al(tBu-salen)]2O, coordinating to water, dioxane and 1,2-epoxyhexane. Coordinated epoxyhexane was activated towards ring-opening, to give various species which remained coordinated to the aluminium centers. The protonated [Al(tBu-salen)]2O complexes catalysed the synthesis of cyclic carbonates from epoxides and carbon dioxide both in the presence and absence of tetrabutylammonium bromide as a nucleophilic cocatalyst. The catalytic activity was principally determined by the nature of the nucleophilic species within the catalyst structure rather than by changes to the Lewis acidity of the metal centers.
Fig. 2 (A) Stepped and bowl conformations of a salen ligand within a metal(salen) complex. (B) Illustration of substituents (R1) in axial or equatorial positions. |
A metal ion coordinated to a salen ligand is most commonly six-coordinate with two additional ligands (X and Y) also coordinated to the metal to give an octahedral geometry. However, depending on the metal and its oxidation state, four-coordinate4 and five-coordinate5 complexes can also be formed and for larger metals, higher coordination-numbers are possible.6 Within an octahedral, six-coordinate salen complex, there are three theoretically possible configurations for the salen ligand: trans, cis-α and cis-β as shown in Fig. 3.7 The trans-configuration is by far the most common, but in complexes composed of a salen ligand and a bidentate ligand, the salen ligand adopts the cis-β configuration.8 Complexes with a trans-configuration are achiral whilst complexes with cis-α or cis-β configurations are inherently chiral, giving rise to Δ and Λ stereoisomers.7
In recent years, we have worked extensively on five-coordinate aluminium complexes of salen and related ligands, showing that complexes 1–5 (Fig. 4) formed active catalysts for: the synthesis of cyclic carbonates from epoxides and carbon dioxide9–12 (Scheme 1A); the synthesis of oxazolidinones from epoxides and isocyanates13 (Scheme 1B) or from aziridines and carbon dioxide14 (Scheme 1C); the synthesis of di- and tri-thiocarbonates from epoxides and carbon disulfide15 (Scheme 1D) and asymmetric cyanohydrin synthesis16 (Scheme 1E). Complex 1 has also been used by other researchers to catalyse Michael additions3 (Scheme 1F) and Passerini-type reactions17 (Scheme 1G). Aluminium(salen) complexes in general have been widely used to initiate ring-opening polymerisation of cyclic esters.18
In contrast to six-coordinate metal(salen) complexes, the structures and structural dynamics of five-coordinate metal(salen) complexes have not previously been analysed in detail. This is crucial information needed to facilitate the design of highly active catalysts based on five-coordinate complexes. Therefore, in this paper we analyse the solid and solution state structures of bimetallic aluminium(salen) complex 1 and related complexes and show that the complexes possess dynamic structures, interconverting between square-based pyramidal and trigonal bipyramidal geometries. The ability of the complexes to catalyse the synthesis of styrene carbonate from styrene oxide and carbon dioxide is also compared.
Fig. 5 (a) structure of complex 1.19 (b) structure of complex 1·HCl. |
The single-crystal X-ray structure‡ of 1·HCl (Fig. 5b and ESI†) showed major differences compared to that of unprotonated 1. The additional proton is localised on the bridging oxygen, resulting in the Al–O–Al bond angle reducing to 153.17(11)°. One aluminium atom is six-coordinate (with a water occupying the sixth coordination site hydrogen-bonded to the chloride anion) whilst the other aluminium atom remains five-coordinate. There is also a marked lengthening in the aluminium to bridging oxygen distances. In complex 1 these are 1.6827(6) and 1.6842(6), whereas for complex 1·HCl the distances are 1.8112(17) to the five-coordinate aluminium and 1.9407(18) to the six-coordinate aluminium.
The salen ligand associated with the six-coordinate aluminium atom is pushed into a more equatorial plane relative to that in unprotonated complex 1 and this in turn makes the coordination geometry of the salen ligand attached to the five-coordinate aluminium more trigonal bipyramidal in complex 1·HCl (τ5 = 0.63) than in complex 1 (τ5 = 0.03 and 0.46 for the two crystallographically unique molecules).20 O6 and N3 form the two apices (N3–Al2–O6 angle 168.39(8)°) and O4, O5 and N4 form the central triangle (O4–Al2–N4 angle 118.14(8)°, O4–Al2–O5 angle 110.80(8)° and N4–Al2–O5 angle 130.62(9)°). This effectively blocks the potential sixth coordination site associated with this aluminium atom and prevents it from becoming six-coordinate.
The structural features of the X-ray structure of complex 1·HCl correlate very well with the previously reported results of DFT calculations on the interaction of complexes 2 and 3 (Fig. 4) with carbon dioxide to give adducts 6 and 7 respectively (Fig. 6).11 In complexes 6 and 7, the carbon dioxide was found to interact with the μ-oxo-bridging oxygen, giving Al–O–Al bond angles of 138–145° compared to an Al–O–Al bond angle of 152° in the X-ray structure of complex 2.21 It was also calculated that the aluminium atoms in complex 7 had increased Lewis acidity compared to those in complex 3, and would form a mono-adduct with ethylene oxide. These calculations and associated experimental results allowed us to propose a mechanism by which complexes 1–3 can catalyse the formation of cyclic carbonates from epoxides and carbon dioxide in the absence of a nucleophilic cocatalyst.11
Fig. 7 The aromatic and imine region of the 1H NMR spectra of compounds 1 (red), 1·TFA (green) and 8 (blue) recorded at 400 MHz in CDCl3 at 298 K. |
Fig. 8 The tert-butyl group region of the 1H NMR spectra of 1·TFA recorded at 500 MHz in CDCl3 at 233–328 K. |
The temperature dependent changes in the tert-butyl region of the NMR spectra of 1·TFA are mirrored in the signals present in other regions of the spectra. Thus, the four aromatic and two imine signals present at temperatures below 273 K merge into two aromatic signals and one imine signal at temperatures of 303 K and above. The spectra also show a highly temperature dependent OH signal which appears at 5.7 ppm at 233 K, shifting and broadening to 4.1 ppm at 303 K before becoming too broad to detect at higher temperatures.
Line shape analysis§ of the tert-butyl signals in the variable temperature NMR spectra of 1·TFA was carried out to allow the rate constant of the exchange process and the Gibbs energies of activation (ΔG‡) to be determined at each temperature (see ESI†). The two sets of tert-butyl signals (a, b and c, d) were modelled separately as non-coupled two spin systems and gave mutually consistent data. The rate constants for the exchange process were found to increase from 0.5–1.5 s−1 at 233 K to 4300–9000 s−1 at 328 K, but the corresponding Gibbs energies of activation were temperature independent with a value of 56.9 ± 1.3 kJ mol−1 at all twelve temperatures and for both sets of data. Eyring plots of ln(k/T) against 1/T (Fig. 9) were linear for both data sets and allowed the enthalpy (ΔH‡) and entropy (ΔS‡) of activation to be determined as 59.0 ± 3.2 kJ mol−1 and 0.0 ± 0.1 J mol−1 K−1 respectively. The zero value for ΔS‡ is consistent with the lack of temperature dependency of ΔG‡ and indicates that the process which causes the signals of the tert-butyl groups within 1·TFA to exchange position occurs without a significant change in entropy and so is likely to be an intramolecular rearrangement.
Addition of two equivalents of trifluoroacetic acid to complex 1 resulted in a resharpening of the 1H NMR peaks to positions that differed from those of compound 1 (Fig. 7). The structure of the species formed on treatment of compound 1 with two equivalents of trifluoroacetic acid was shown to be mononuclear aluminium(tBu-salen) trifluoroacetate 8 (Scheme 3) by high resolution field desorption mass spectrometry. However, the room temperature 1H NMR spectrum of complex 8 suggested a C2-symmetric structure. Therefore, a VT NMR study of complex 8 was carried out in deuterated chloroform between 218 and 328 K (see ESI†). At the lowest temperatures, the imine, aromatic and tert-butyl signals all resolved into two separate peaks; confirming that the complex actually had C1-symmetry. For compound 8, line shape analysis§ of the imine and aromatic signals in the variable temperature NMR spectra was carried out (see ESI†) as these underwent more changes than the tert-butyl signals. The imine signals and aromatic hydrogens ortho- and para-to the imine were modelled separately to give three sets of data, all of which were mutually consistent. The Gibbs energies of activation were again temperature independent with a value of 49.0 ± 1.0 kJ mol−1 for all 30 data points. Eyring plots of ln(k/T) against 1/T (Fig. 9) were linear and allowed the enthalpy (ΔH‡) and entropy (ΔS‡) of activation to be determined as 48.9 ± 0.3 kJ mol−1 and −0.2 ± 3.2 J mol−1 K−1 respectively. The approximately zero value for ΔS‡ again indicates that the process which causes the aromatic and imine signals within 8 to exchange position is likely to be an intramolecular rearrangement. The chemistry occurring on treatment of complex 1 with trifluoroacetic acid is therefore summarised in Scheme 3.
The exchange process which results in complexes 1·TFA and 8 appearing to be C2-symmetrical at higher temperatures can be explained by the process shown in Scheme 4. Borrowing terminology used in octahedral, six-coordinate complexes,7 a square pyramidal complex I has a salen ligand in the trans-configuration and a vacant coordinate site opposite the X-ligand. Movement of one of the salen ligand's oxygen atoms into this vacant site generates trigonal bipyramidal complex II. The X-ray structures of complexes 1 and 1·HCl provide good evidence for the existence of both of these coordination geometries. Subsequent migration of the X ligand to the free coordination site within complex II generates a new square pyramidal complex in which the salen ligand has a cis-β configuration. There are many examples of octahedral metal(salen) complexes with a salen ligand in the cis-β configuration.8 Movement of the remaining equatorial oxygen atom of the salen ligand into the vacant apical coordination site of complex III generates a new trigonal bipyramidal complex IV. Subsequent migration of the other apically coordinated oxygen of the salen ligand to an equatorial position generates square based pyramidal complex V in which the salen ligand again has a cis-β configuration, but with a different oxygen atom in the apical position compared to complex III. Migration of the X ligand into the free apical coordination site of complex V generates trigonal bipyramidal complex VI and finally migration of the remaining apically coordinated oxygen of the salen ligand in complex VI to an equatorial position generates square based pyramidal complex VII with a trans-configuration of the salen ligand. In complex VII, the X ligand is coordinated to the opposite face of the square planar aluminium(salen) unit compared to complex I, so that a time-averaged structure would appear to be C2-symmetric.
The pathway shown in Scheme 4 is fully consistent with the activation parameters determined by line-shape analysis of the variable temperature NMR data. No ligand dissociation or association occurs, so the entropy of activation would be expected to be close to zero. The X group in compound 8 is a trifluoroacetyl group, whilst for 1·TFA the X group is a much larger OAl(salen) unit. The rearrangement shown in Scheme 4 involves the X group moving into the equatorial plane of square based pyramidal complexes III and V where steric interactions with the salen ligand will be greater than for structures I and VII where the X group is in the apical position of a square based pyramid. This accounts for the higher values of the enthalpy and Gibbs energy of activation associated with the rearrangement of complex 1·TFA compared to complex 8.
Close examination of the 1H NMR spectrum of compound 1 (Fig. 7 and ESI†) showed that in addition to the major, apparently C2-symmetrical, species, a second, lower intensity set of signals corresponding to a C1-symmetrical complex were present. This is apparent in Fig. 7, where in addition to the three major aromatic/imine peaks, six other signals are present. In this case, all peaks are sharp and well resolved suggesting that at room temperature they exchange only very slowly if at all. A variable temperature NMR study (298–328 K in deuterated chloroform) revealed that the spectra of both the major and minor species were temperature dependent. In this case, although the peaks did undergo changes in chemical shift, they did not coalesce in the accessible temperature range. However, the relative amount of the minor species increased from 9% at 298 K to 14% at 328 K. Thus, the minor peaks present in the 1H NMR spectrum are consistent with complex 1 in which one of the salen ligands is in a trigonal bipyramidal geometry as observed for one of the two independent molecules in the crystal structure of complex 1.19 This interpretation was supported by a DOSY experiment (in CDCl3) which showed that the major and minor species had very similar diffusion coefficients of 5.4 × 10−10 m2 s−1 and 5.1 × 10−10 m2 s−1 respectively (see ESI†). These compare with a value of 2.0 × 10−9 m2 s−1 for the chloroform present in the NMR solvent.
Protonation of complex 1 using a solution of anhydrous hydrogen chloride in dioxane gave more complex results as the dioxane acted as a Lewis base. Addition of one equivalent of hydrogen chloride to complex 1, followed by evaporation of the excess dioxane in vacuo cleanly gave complex 9 (Scheme 5). The 1H NMR spectrum of complex 9 (at room temperature) suggested that the complex was C2-symmetric, but the broadness of the signals again indicated that this was due to a dynamic process (Fig. 10 and ESI†). The residual dioxane signal integrated to eight protons, indicating that just one dioxane was coordinated within complex 9. The structure of complex 9 exactly mirrors the structure of 1·HCl determined by X-ray crystallography (Fig. 5b) with the water molecule replaced by a dioxane ligand.
Fig. 10 Extracts of the 1H NMR spectra of compounds: 1 (red); 9 (green); 1:1.25 mixture of 10 and 11 (cyan); and 11 (purple) in CDCl3. |
In contrast to the treatment of complex 1 with two equivalents of trifluoroacetic acid, addition of two equivalents of hydrogen chloride in dioxane to complex 1, followed by removal of excess dioxane in vacuo resulted in the formation of two new species 10 and 11 in a 1:1.25 ratio (Fig. 10). In addition to the imine and aromatic signals shown in Fig. 10, the full 1H NMR spectrum (see ESI†) showed a broad OH peak at 4.8 ppm; evidence for coordinated dioxane in complex 11; and the expected cyclohexyl and tert-butyl protons.
To confirm the structures of complexes 10 and 11, an alternative synthesis of these species was undertaken. Thus, treatment of the tBu-salenH2 ligand with diethylaluminium chloride gave the known12 five-coordinate Al(tBu-salen)Cl complex (Scheme 5). Addition of excess dioxane to a sample of Al(tBu-salen)Cl formed the dioxane solvate {[Al(tBu-salen)(dioxane)2]+ Cl−} in situ. The 1H NMR spectra of this solvate did not match those of complexes 10 and/or 11 (see ESI†). However, after evaporation of excess dioxane from the solvate, the 1H NMR spectrum did match that of complexes 10 and 11 obtained from complex 1, though with a 1:2.5 ratio of 10:11 (see ESI†).
Treatment of bimetallic complex 1 with anhydrous hydrogen chloride to give products in which the μ-oxo bridge has been broken will produce half an equivalent of water relative to the concentration of aluminium. Therefore, a 1:1 ratio of complexes 10 and 11 would be expected to form when complex 1 was treated with two equivalents of anhydrous hydrogen chloride and the observed ratio was 1:1.25. In contrast, no water is generated when Al(tBu-salen)Cl is treated with dioxane. Hence, the formation of complex 10 under these conditions must be due to adventitious water in the reaction and this accounts for the lower amount of complex 10 formed by this route. By carrying out the synthesis from Al(tBu-salen)Cl under rigorously anhydrous conditions with evaporation of excess dioxane on a Schlenk line, the formation of complex 10 could be completely avoided and only complex 11 was formed (Fig. 10 and ESI†). The 1H NMR spectrum of pure complex 11 confirmed that half a dioxane molecule was present for each Al(tBu-salen) unit.
As shown in Fig. 10, the 1H NMR signals for complex 11 in the mixture of species 10 and 11 do not exactly superimpose with the signals observed when only species 11 was present. However, a NOESY spectrum recorded on a sample with a 1:2.5 ratio of complexes 10 and 11 showed cross-peaks between the signals for each species, indicating that they were in chemical exchange with each other (see ESI†). Thus, slightly different chemical shifts and line widths would be expected for complex 11 in the presence and absence of complex 10.
It was apparent from the room temperature 1H NMR spectra of compounds 10 and 11 that aspects of their structures were again not fully explained by the spectra. In particular, the aromatic signals shown in Fig. 10 were far simpler than would be expected and the imine signals in Fig. 10 appeared extremely broad or to be split into two separate peaks. Therefore a variable temperature 1H NMR study was undertaken on the 1:2.5 mixture of 10 and 11 in deuterated chloroform at 500 MHz between 218 and 328 K. Fig. 11 shows the tert-butyl region of the resulting spectra and the full spectra are given in the ESI.† At 218 K, eight tert-butyl signals (labelled a–h) are present between 1.55 and 0.95 ppm. This is the number expected for a combination of complexes 10 and 11 as within each of these complexes the aluminium(tBu-salen) units are not C2-symmetric. However, as the temperature increases, the tert-butyl signals start to merge, first to six signals at 243–253 K, then to two signals (one of which is very broad) at 313 K. Similar changes are apparent in other regions of the spectra (see ESI†). The signal for the coordinated water molecule of complex 10 undergoes a particularly large change in chemical shift: from 5.75 ppm at 218 K to 3.20 ppm at 328 K.
Fig. 11 Stacked plot of extracts of the 500 MHz 1H NMR spectra of a 1:2.5 mixture of compounds 10 and 11 in CDCl3 recorded at 218 to 328 K. |
The eight tert-butyl signals could be divided into two groups of four (a–d and e–h) each of which merges to a single peak at the higher temperatures and which correspond to the tert-butyl groups ortho- and para-to the phenols in the salen ligand. These two sets of tert-butyl signals were separately subjected to line shape analysis§ (using a four non-coupled spin model, see ESI†) to allow rate constants and Gibbs energies of activation to be determined at each temperature. For this system, ΔG‡ was temperature dependent, increasing steadily from 50.7 kJ mol−1 at 218 K to 67.6 kJ mol−1 at 328 K based on analysis of signals a–d and from 52.8 kJ mol−1 at 218 K to 69.5 kJ mol−1 at 328 K based on analysis of signals e–f. Eyring plots for the two sets of data are given in Fig. 12 and allowed ΔH‡ to be calculated as 17.9 ± 1.1 kJ mol−1 and ΔS‡ to be determined as −155 ± 1 J mol−1 K−1.
Within the mixture of compounds 10 and 11, three separate exchange processes will occur. Both compounds can independently undergo the same salen ligand rearrangement discussed above for compounds 1·TFA and 8 and illustrated in Scheme 4. This intramolecular rearrangement does however, require the initial dissociation of a weakly bound water or dioxane ligand to generate a five-coordinate complex and hence will have a positive entropy of activation. Compounds 10 and 11 also exchange their weakly bound water and dioxane ligands as illustrated in Scheme 6 and the negative value observed for ΔS‡ suggests that this occurs through an associative mechanism such as that shown in the transition state structure in Scheme 6. The associative ligand exchange outweighs the dissociative ligand rearrangement, resulting in an overall negative entropy of activation.
Addition of excess 1,2-epoxyhexane to a solution of (tBu-salen)AlCl in deuterated chloroform resulted in smaller shifts to the 1H NMR aromatic and epoxide signals (see ESI†). These were accompanied by the appearance of multiple new signals in the range of 3–4 ppm and 6.5–9 ppm, indicative of the epoxide having undergone ring–opening to form diol and oligomeric ethers which compete with the 1,2-epoxyhexane for coordination to the aluminium. Consistent with this, when the excess 1,2-epoxyhexane was evaporated, the aromatic signals did not revert to their original shifts and the multiple peaks at 3–4 ppm were still present in the 1H NMR spectrum. There is literature precedent for aluminium(salen) complexes initiating the ring-opening polymerisation of epoxides.22
When excess 1,2-epoxyhexane was added to 1·TFA, no changes in the 1H NMR chemical shifts of the aromatic or epoxide hydrogens was observed, though the aromatic and imine signals did become sharper (see ESI†). On evaporation of excess 1,2-epoxyhexane, changes in the aromatic and imine signals did become apparent. In addition to the three signals at the original positions, new signals corresponding to a salen ligand in a non-C2 symmetric environment appeared as did peaks between 3 and 4 ppm in the 1H NMR spectrum and between 65 and 75 ppm in the 13C NMR spectrum corresponding to ring–opened epoxide. These results can be explained on the basis that 1,2-epoxyhexane undergoes ring–opening as the solution is being evaporated to give oligomeric ethers22 which coordinate to one of the aluminium centres of 1·TFA, forming a six-coordinated aluminium which can no longer undergo the salen ligand rearrangement shown in Scheme 4. A very similar situation was observed when 1,2-epoxyhexane was added to complex 9, though in this case a small change in the chemical shift of the epoxide signals was seen (see ESI†). On evaporation of the 1,2-epoxyhexane, the dioxane initially weakly coordinated to complex 9 was also removed. These results indicate that complexes 1, 1·TFA, 9 and (tBu-salen)AlCl are all capable of acting as Lewis acids towards 1,2-epoxyhexane and in the case of 1·TFA, 9 and (tBu-salen)AlCl this activation of the epoxide results in its ring–opening by a nucleophile present in the reaction to give oligomers22 which also coordinate to the aluminium(salen) units.
Entry | Aluminium complex (mol%) | Bu4NBr (mol%) | T (°C) | P (bar) | Conversiona or (isolated yield) |
---|---|---|---|---|---|
a Determined by 1H NMR analysis of the reaction mixture. b 5 mol% of dioxane added. c 1·TFA was formed in situ by addition of TFA (2.5 mol%) to complex 1 (2.5 mol%) prior to addition of Bu4NBr. d Complex 8 (5 mol%) was formed in situ by addition of TFA (5.0 mol%) to complex 1 (2.5 mol%) prior to addition of Bu4NBr. | |||||
1 | None | 2.5 | 25 | 1 | 0 |
2 | 1 (2.5) | 0 | 25 | 1 | 9 |
3 | 1 (2.5) | 2.5 | 25 | 1 | 53 |
4 | 1b (2.5) | 2.5 | 25 | 1 | 55 |
5 | 9 (2.5) | 2.5 | 25 | 1 | 46 |
6 | 1·TFA (2.5) | 2.5 | 25 | 1 | 36 |
7 | 1·TFAc (2.5) | 2.5 | 25 | 1 | 48 |
8 | 8 (2.5) | 2.5 | 25 | 1 | 27 |
9 | 8d (5.0) | 2.5 | 25 | 1 | 11 |
10 | None | 0 | 100 | 50 | 0 |
11 | 1 (2.5) | 0 | 100 | 50 | (59) |
13 | 1·TFA (2.5) | 0 | 100 | 50 | (29) |
12 | 9 (2.5) | 0 | 100 | 50 | (40) |
14 | 8 (2.5) | 0 | 100 | 50 | (7) |
The results presented in entries 3–7 of Table 1 suggest that it is the nucleophile (tetrabutylammonium bromide) rather than the Lewis acid that is the dominant factor in determining the effectiveness of a tetrabutylammonium bromide/bimetallic aluminium(salen) complex catalyst system. Therefore, 1, 1·TFA, 8 and 9 were tested as catalysts under alternative, tetrabutylammonium bromide free conditions at 100 °C and 50 bar carbon dioxide pressure11 (Scheme 7, conditions B). Entry 10 shows that under these conditions, no reaction occurs in the absence of a catalyst. Complex 1 shows reasonable catalytic activity under these reaction conditions (entry 11). Protonation of complex 1 with trifluoroactic acid to form 1·TFA or with HCl to form complex 9 reduced the catalytic activity (entries 12 and 13). The significantly higher catalytic activity of complex 9 compared to 1·TFA can be explained by the presence of a reasonable nucleophile (chloride) in complex 9 but not in complex 1·TFA. In the presence of chloride two catalytic cycles are possible under these reaction conditions, involving epoxide ring-opening by chloride or carboxylate as previously determined.9–11,19 The lower catalytic activity of both complexes 9 and 1·TFA compared to complex 1 is consistent with the need for the μ-oxo group of the complexes to interact with carbon dioxide (as shown in Fig. 6) during the catalytic cycle in the absence of a nucleophilic cocatalyst.10,11 Protonation of the μ-oxo group will inhibit this interaction. Finally, entry 14 shows that monometallic complex 8 is again a very poor catalyst under these conditions.
Protonation of μ-oxo bridged bimetallic aluminium(salen) complexes occurs on the bridging oxygen and results in significant changes to the coordination geometry and ligand conformations around the aluminium centres. Protonation also increases the Lewis acidity of the aluminium centres as shown by their interaction by Lewis bases such as water, dioxane and 1,2-epoxyhexane. However, the protonated complexes have lower catalytic activity than the unprotonated complex for the synthesis of styrene carbonate from styrene oxide and carbon dioxide which suggests that nucleophilicity (of a cocatalyst or the μ-oxo bridge) is more important than Lewis acidity for the catalytic activity.
Footnotes |
† Electronic supplementary information (ESI) available: X-ray data and copies of all recorded and simulated spectra. CCDC 2022416. For ESI and crystallographic data in CIF or other electronic format see DOI: 10.1039/d0dt03598j |
‡ X-ray data for complex 1·HCl has been deposited with the CCDC 2022416.† |
§ Line shape analysis was carried out using WinDNMR (https://www.chem.wisc.edu/areas/reich/plt/windnmr.htm). |
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