Frustrated Lewis pairs incorporating the bifunctional Lewis acid 1,1′-fc{B(C₆F₅)₂}₂: reactivity towards small molecules

Abstract

Applications of the bifunctional ferrocenediyl Lewis acid 1,1′-fc{B(C₆F₅)₂}₂ in frustrated Lewis pair (FLP) chemistry are described. The coordination (or otherwise) of a range of sterically encumbered C-, N- and P-centred Lewis bases has been investigated, with lutidine, tetramethylpiperidine, PPh₃, P^tBu₃ and the expanded ring carbene 6Dipp being found to be sterically incapable of coordinate bond formation. The chemistry of a range of these FLPs in the presence of H₂O, NH₃, CO₂ and cyclohexylisocyanate (CyNCO) has been investigated, with the patterns of reactivity identified including simple coordination chemistry, E–H bond cleavage and C–B insertion.

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Introduction

The exploitation of frustrated Lewis pairs (FLPs) constitutes a significant development in the fields of small molecule activation and catalysis over the past decade.^1–3 The cooperative use of sterically unquenched Lewis acid and Lewis basic sites facilitates transformations more typically associated with transition metal complexes.³ Since the first example of their use in the heterolytic cleavage of H₂ was described in 2006,² numerous applications have been reported in the activation of other E–H bonds (e.g. E = B, C, N, O, Si), and in the binding of small molecules, including atmospheric oxides (such as CO, CO₂, NO, N₂O, and SO₂).³ While the Lewis acid component of a large number of these FLP systems is the commercially available perfluoroaryl borane B(C₆F₅)₃, examples featuring other neutral boranes,⁴ heavier Group 13 analogues,⁵ borenium cations,⁶ and Lewis acids from the d-block have also emerged.⁷

FLPs that contain a ferrocenyl reporter unit offer the possibility for inducing a measurable electrochemical and/or colorimetric response on small molecule capture,^8,9 and therefore have potential uses in detection. Two approaches in this area are exemplified by the Fe(η⁵-C₅Ph₅)(η⁵-C₅H₄P^tBu₂)/B(C₆F₅)₃ system in which the Lewis basic phosphine unit contains a ferrocenyl substituent,¹⁰ and by recent work from our laboratory utilizing the ferrocenyl borane Fe(η⁵-C₅H₅){η⁵-C₅H₄B(C₆F₅)₂} [= FcB(C₆F₅)₂, 1],¹¹ a compound which was previously reported by Piers and co-workers.^12a In terms of small molecule capture, the P^tBu₃/1 FLP binds N₂O intact to generate the ambiphilic adduct ^tBu₃P·N₂O·1 (Scheme 1); while similar chemistry also occurs with P^tBu₃/B(C₆F₅)₃, the formation of ^tBu₃P·N₂O·1 is signalled by a maroon-to-amber colour change and a shift of 300 mV in the Fe^II/III redox potential.^11,13

Scheme 1 Binding of N₂O by FLPs featuring P^tBu₃ and either B(C₆F₅)₃ or 1.^11,13

Although this N₂O detection protocol illustrates the potential of ferrocenyl boranes in FLP chemistry, we wanted to probe the broader scope of this approach, by exploiting other boranes incorporating metallocene scaffolds. In particular, we hypothesized that 1,1′-fc{B(C₆F₅)₂}₂ (2) might be of interest, due to (i) its potential to act as a bifunctional (potentially chelating) Lewis acid to trap substrates bearing geometrically divergent Lewis basic sites; and (ii) its stronger Lewis acidity, in comparison to monofunctional 1 (Fig. 1).¹² This observation reflects the π electron-withdrawing nature of the additional –B(C₆F₅)₂ group, and the fact that through-space donation from the electron-rich iron centre to the individual pendant borane function(s) is less pronounced when there are two such groups.¹²

Fig. 1 Ferrocenyl and ferrocene-diyl based Lewis acids FcB(C₆F₅)₂ (1) and 1,1′-fc{B(C₆F₅)₂}₂ (2) [Fc = Fe(η⁵-C₅H₅)(η⁵-C₅H₄); 1,1′-fc = Fe(η⁵-C₅H₄)₂].

With this in mind, we set out to explore the potential for 2 to act as the Lewis acid component in FLPs featuring a range of C-, N- and P-donors, and subsequently to probe the use of such systems in the activation of small molecules such as H₂O, NH₃ and CO₂. We report the results of these studies in this manuscript.

Results and discussion

Alternative synthesis of 1,1′-fc{B(C₆F₅)₂}₂ (2)

Piers and co-workers have reported the synthesis of 2 from 1,1′-fc(HgCl)₂ and ClB(C₆F₅)₂ (Scheme 2).^12b Generation of the ClB(C₆F₅)₂ precursor involves the synthesis of Me₂Sn(C₆F₅)₂ from LiC₆F₅, and its subsequent reaction with BCl₃ at elevated temperature/pressure.^12c With this in mind, a more direct synthesis from LiC₆F₅ was targeted, drawing on the route which we have previously developed to prepare 1 from FcBBr₂ (Scheme 3).¹⁴ The one-pot literature synthesis of bifunctional 1,1′-fc(BBr₂)₂ from ferrocene and BBr₃,¹⁵ is followed by reaction with slightly greater than four equivalents of LiC₆F₅, generated in situ from ⁿBuLi and C₆F₅Br. Although LiC₆F₅ is notoriously explosive above −40 °C,¹⁶ the synthetic protocol that we employ means that [as in the synthesis of Me₂Sn(C₆F₅)₂] it never warms above −78 °C, and so can be safely and reproducibly used in the synthesis of 2. Following this procedure, 2 can be isolated after extraction into hot hexane with a yield (ca. 50%) broadly comparable to that reported by Piers (up to 40%).^12b

Scheme 2 Literature synthesis of 1,1′-fc{B(C₆F₅)₂}₂ (2).^12b

Scheme 3 (upper) Synthesis of 1 from FcBBr₂, and (lower) modification for the synthesis of 2 from 1,1′-fc(BBr₂)₂. Caution: The reaction temperature must be kept below −40 °C at all times when handling LiC₆F₅.

Interaction of Lewis bases with 2

The sterically unencumbered tertiary phosphine Me₃P is known to form a 2 : 1 adduct with 2, through the formation of two P→B coordinate bonds.^12b The donor/acceptor chemistry of 1 has been explored in greater depth,^11a and the combination with the much bulkier P^tBu₃, for example, is known to constitute an FLP. With this in mind, the interaction of 2 with a range of bulky C-, N- and P-donor Lewis bases was investigated, with the aim of identifying FLP systems for further reactivity studies.

N-Heterocyclic carbenes. 1 has previously been shown to form classical Lewis acid–base adducts with the bulky N-aryl substituted imidazolylidene donors IMes and IDipp, together with the less strongly donating, backbone-chlorinated carbene IMesCl₂ (Fig. 2).^11a These NHCs were therefore thought to provide a suitable comparative starting point for the exploration of the coordination behaviour of 2. In addition, the behaviour of 2 in the presence of the more sterically encumbered (and more strongly σ-donating) expanded ring systems 6Mes and 6Dipp was also to be probed.¹⁷

Fig. 2 N-Heterocyclic carbenes (NHCs) utilized in the current study.

The addition of IMes to 2 in a 2 : 1 molar ratio results in an immediate colour change from violet to orange, and the appearance of a ¹¹B NMR resonance at δ_B = −14 ppm, consistent with the formation of a tetra-coordinate borate through coordination of the IMes donor.^11a1H NMR spectroscopy suggests that two molecules of NHC have been assimilated and that the ‘normal’ C2-mode of carbene binding pertains, with signals at δ_H = 7.46 and 7.59 ppm corresponding to the backbone N(CH)₂N protons (albeit with loss of the plane of symmetry). The formation of a low symmetry adduct is also consistent with the observation of ten distinct signals in the ¹⁹F NMR spectrum (indicating that the equivalence between the ortho, meta and para fluorines of the two perfluorophenyl rings had been lost); a similar pattern of ¹⁹F signals is observed in the ¹⁹F spectrum of the corresponding monofunctional adduct 1·IMes, and has been ascribed to restricted rotation about the sterically congested B–C bonds on the timescale of the NMR experiment.^11a

In the case of 2, the molecular structure derived from X-ray crystallography confirms the formulation of the adduct as 1,1′-fc{B(C₆F₅)₂·IMes}₂ (2·(IMes)₂, Fig. 3). The solid-state structure possesses approximate (non-crystallographic) C₂ symmetry, and the fact that this adduct displays the same number of ¹⁹F NMR resonances as 1·IMes presumably reflects a similar symmetry relationship between the two –B(C₆F₅)₂·IMes functions in solution. Bond metrics associated with the borate functions (for example B–C distances) are essentially identical to those measured for 1·IMes,^11a reflecting the fact that there is relatively little geometric perturbation around the boron centre induced by the presence of the second borate function.

Fig. 3 Molecular structures of (left) 1,1′-fc{B(C₆F₅)₂·IMes}₂, 2·(IMes)₂ and (right) 1,1′-fc{B(C₆F₅)₂·NH₃}₂, 2·(NH₃)₂, with thermal ellipsoids set at the 35% probability level. Selected hydrogen atoms and solvate molecules omitted and mesityl groups shown in wireframe format for clarity. Selected bond lengths (Å) and angles (°): [for 2·(IMes)₂] B(4)–C(60) 1.675(5), B(4)–C(3) 1.638(5), B(4)–C(14) 1.666(5), B(4)–C(47) 1.676(5), C(3)–B(4)–C(14) 113.9(3), C(3)–B(4)–C(47) 106.0(3), C(14)–B(4)–C(47) 111.2(3); [for 2·(NH₃)₂] B(7)–N(8) 1.624(2), B(7)–C(5) 1.601(2), B(7)–C(9) 1.648(2), B(7)–C(20) 1.639(2), B(36)–N(37) 1.627(2), B(36)–C(32) 1.600(2), B(36)–C(38) 1.649(2), B(36)–C(49) 1.638(2), C(5)–B(7)–C(9) 115.9(1), C(5)–B(7)–C(20) 113.3(1), C(9)–B(7)–C(20) 106.5(1), C(32)–B(36)–C(38) 114.4(1), C(32)–B(36)–C(49) 114.4(1), C(38)–B(36)–C(49) 108.9(1).

The reaction between IMes and 2 was also examined in a 1 : 1 molar ratio. However, monitoring by ¹⁹F NMR suggests that this results in the formation of a mixture of the 1 : 1 adduct, the 2 : 1 adduct [i.e.2·(IMes)₂], and unreacted borane starting material. Ten resonances due to 2·(IMes)₂ are observed, alongside signals corresponding to the free Lewis acid and further signals, presumed to be derived from the 1 : 1 adduct. This inference is supported by the ¹¹B NMR spectrum, which features a sharp signal at −13.7 ppm, consistent with the borate functions in the 2 : 1 adduct, alongside a broad signal consistent with uncomplexed three-coordinate borane centres. The observation of a mixture of products suggests that IMes binding at the two borane functions is essentially independent, consistent with the conformationally flexible nature of the ferrocenediyl core.

Given the diagnostic nature of the ¹¹B and ¹⁹F signals associated with adduct formation, these measurements were then used to determine the course of the reactions of 2 with other NHCs. Thus, signals in the range δ_B = −10 to −13 ppm were observed on addition of two equivalents of IMesCl₂, IDipp or 6Mes (with the solution in each case turning an orange colour), with the respective ¹⁹F NMR spectra displaying a similar ten-resonance pattern to that measured for 2·(IMes)₂. By contrast, on addition of 6Dipp to 2, the deep maroon colour of the solution is retained, and ¹H, ¹¹B and ¹⁹F NMR spectra could be used to establish that no substantive reaction has taken place. In particular, the ¹¹B and ¹⁹F signals are unshifted from those of the starting material 2, and the ¹H NMR spectrum consists of the superposition of the signals due to 6Dipp and 2. In this case alone it appears that the NHC and 2 constitute an unquenched FLP, an observation consistent with the larger steric demands of the 6Dipp ligand (%V_bur = 50.8 vs. 36.5, 44.5 and 42.2 for IMes, IDipp and 6Mes).^18,19

Nitrogen and phosphorus-centred donors. We have also probed the interactions of a range of tertiary phosphines and bulky N-donor Lewis bases with 2. Both lutidine (2,6-dimethylpyridine) and tetramethylpiperidine give rise to FLPs in benzene-d₆ solution, as do PPh₃ and P^tBu₃, the latter two being characterized by unchanged ³¹P resonances at −5.4 and 61.9 ppm, respectively. By contrast, the combination of 2 and PⁿBu₃ can be shown to result in an immediate reaction, and multinuclear NMR studies are consistent with classical adduct formation. The single broad peak at δ_B = −11.0 ppm is indicative of a four-coordinate borate centre, and the signal at δ_P = −2.9 ppm is consistent with the ³¹P shift measured for the known compound ⁿBu₃P·B(C₆F₅)₃.²⁰ The chemical shift difference between the meta and para¹⁹F NMR signals, Δδ_m,p is known to decrease on quaternization at boron, and has therefore been widely used to probe the interactions of Lewis bases with boranes containing the B(C₆F₅) moiety.²¹ In this case, the decrease in the value of Δδ_m,p determined from ¹⁹F NMR (from 10.7 ppm for 2 to 5.8 ppm) also supports the idea that a classical phosphine–borane adduct has been formed.

The combination of PCy₃ and 1 has previously been shown by in situ NMR measurements to result in the formation of an FLP in benzene-d₆ solution.^11a However, evidence can also be obtained for the formation of a minor co-product over a period of ca. 2 weeks at room temperature (Scheme 4a). Although the overwhelmingly dominant species present in solution at this point are still 1 and PCy₃, the minor product can be crystallized and shown by X-ray crystallography to be the zwitterion Fc{B(F)(C₆F₅)(C₆F₄PCy₃-4)} (3), derived from S_NAr attack by the phosphine at the para position of one of the perfluorophenyl rings of the Lewis acid, with accompanying migration of fluoride to the boron centre (Fig. 4). Spectroscopically, this chemistry is characterised by diagnostic signals in the ¹¹B and ¹⁹F NMR spectra at δ_B = 2.0 ppm and δ_F = −193.7 ppm associated with the boron-bound fluoride, and a shift in the ³¹P NMR spectrum from the free phosphine at δ_P = 9.7 ppm to 39.9 ppm. Very similar NMR signals are observed for the related system derived from the analogous activation of B(C₆F₅)₃, i.e. B(F)(C₆F₅)₂(C₆F₄PCy₃-4) (δ_B = −0.7 ppm, δ_P = 41.6 ppm).²²

Scheme 4 (a) Minor reaction pathway of PCy₃ with 1, proceeding via nucleophilic attack at the para C–F bond of a C₆F₅ group to give 3. (b) Proposed structure of the product of the reaction of 2 with PCy₃.

Fig. 4 Molecular structure of Fc{B(F)(C₆F₅)(C₆F₄PCy₃-4)}, 3, with thermal ellipsoids set at the 35% probability level; hydrogen atoms for clarity. Selected bond lengths (Å) and angles (°): B(7)–F(8) 1.426(2), B(7)–C(3) 1.613(3), B(7)–C(9) 1.660(3), B(7)–C(20) 1.682(3), C(3)–B(7)–C(9) 110.1(2), C(3)–B(7)–C(20) 114.0(2), C(9)–B(9)–C(20) 108.2(2).

The combination of PCy₃ with 2 was therefore investigated in a 2 : 1 molar ratio. While there was no immediate colour change on mixing, ¹H, ¹¹B, ¹⁹F and ³¹P NMR spectra measured after 1 h show that a reaction has taken place. A broad upfield-shifted resonance is observed in the ¹¹B NMR spectrum at δ_B = 2.6 ppm, and a signal at δ_P = 40.1 ppm in the ³¹P NMR spectrum; both are suggestive of an S_NAr type reaction similar to that observed for PCy₃/1. The ¹⁹F NMR spectrum is more complex. In the case of Fc{B(F)(C₆F₅)(C₆F₄PCy₃-4)} (3), six resonances are observed, corresponding to the boron-bound fluoride, the ortho, meta and para fluorines of the unreacted –C₆F₅ moiety, and two signals for the para-C₆F₄PCy₃ moiety. If analogous reactivity were to take place at both borane functions in 2, then either six or twelve signals might be expected, depending on whether the two borate units are symmetry-related on the NMR timescale. On the other hand, if reaction were to take place at only one of the two borane units, then (superficially) nine signals would be expected, with the additional three arising from the perfluoroaryl rings associated with the unreacted borane centre. In this case twelve ¹⁹F signals are observed, but paradoxically, the ¹H and ³¹P NMR data are consistent with the take-up of only one phosphine unit. Half of the added PCy₃ remains unreacted.

Of the twelve ¹⁹F resonances observed, six can readily be assigned to fluorine environments analogous to those in 3, on the basis of their very similar pattern of chemical shifts (including a resonance at −194.9 ppm, indicative of a boron-bound fluoride). The additional six signals, come in three pairs, suggesting that they arise from the ortho, meta and para fluorines of an unreacted – B(C₆F₅)₂ moiety, in which the equivalence of the two perfluoroaryl rings has been lost. Such inequivalence is presumably caused by restricted rotation about the B–C_Cp bond, which might arise either as a result of the increased steric bulk of the peripheral borate centre, or due to an interaction between the borane and the boron-bound fluoride (Scheme 4b). Some evidence for the latter comes from analysis of the magnitude of the Δδ_m,p splittings derived from the ¹⁹F NMR data (using in the case of the –B(C₆F₅)₂ unit, the mean chemical shift difference between meta and para resonances). Δδ_m,p has a value of 10.7 ppm for starting material 2, this being reduced to 4.4 ppm for the C₆F₅ group of the borate function (cf. 3.6 ppm for the analogous C₆F₅ unit in 3). That determined for the –B(C₆F₅)₂ group is 7.2 ppm (i.e. intermediate between borate and ‘free’ borane), and is therefore potentially suggestive of a weak secondary donor/acceptor interaction (Scheme 4b).²³

Interestingly, and in contrast to PCy₃/1, NMR data for PCy₃/2 show no evidence of unreacted 2 (i.e. FLP formation does not occur) – an observation consistent with the enhanced electrophilicity of 2 compared to 1. It is also noteworthy that (despite the 2 : 1 molar ratio) PCy₃ does not appear to react at the second B(C₆F₅)₂ unit in 2. Potentially, this can be attributed to the reduced electrophilicity of the remaining –B(C₆F₅)₂ unit on conversion of the first to an electron-donating fluoroborate function.^9h

Reactions of small molecules with FLPs derived from 2

With the potential for 2 to function as an FLP in conjunction with sterically encumbered bases established, we focused on exploring the chemistry of such systems in small molecule activation. In common with 1, we find that combinations of 2 with any of PPh₃, P^tBu₃, or 6Dipp (or for that matter the N-donors lutidine or tetramethylpiperidine) do not activate H₂ either under ambient conditions or on heating to 350 K. Such observations are consistent with the electron-donating nature of the ferrocenediyl substituent and the consequently reduced Lewis acidity at boron compared to B(C₆F₅)₃.^17,24 As such, we hypothesized that the bifunctional nature of Lewis acid 2 might be better suited to the cleavage (or capture) of small molecules which yield Lewis bases that can be bound in a chelating fashion (Fig. 5). We therefore examined the reactivity of 2 towards H₂O, NH₃ and CO₂ (plus CO₂ surrogates of the type RNCO).

Fig. 5 Postulated binding motifs in small molecule capture/activation using FLPs containing 2.

The combination of 2 and P^tBu₃ reacts very readily with water via O–H bond cleavage. The dark maroon colour of 2 in benzene-d₆ solution turns to a yellow-orange, and over 24 hours the formation of a yellow crystalline product is observed. In situ¹H, ¹¹B, ¹⁹F and ³¹P NMR studies give an indication as to the nature of the reaction taking place. Thus, the ³¹P spectrum shows a single peak at δ_P = 58.3 ppm corresponding to the phosphonium cation, [HP^tBu₃]⁺, and the ¹⁹F NMR spectrum shows three resonances, shifted from those in the starting material, and with a significant decrease in Δδ_m,p compared to 2 (4.4 cf. 10.7 ppm). A large upfield shift in the ¹¹B NMR signal is also observed (to δ_B = 2.0 ppm), characteristic of the transformation of a three-coordinate borane to a four-coordinate borate. Moreover, single crystals suitable for X-ray crystallography could be obtained by recrystallization from chloroform. The solid-state structure so obtained confirms the nature of the product as [HP^tBu₃][1,1′-fc{B(C₆F₅)₂}₂(μ-OH)] (i.e. [HP^tBu₃][2·(μ-OH)]), featuring a hydroxide ion bridging symmetrically between the two boron centres in the anionic component (Scheme 5 and Fig. 6).^25,26 From a geometric perspective, the hydroxide binding motif is similar to that observed in the zwitterionic cobaltocenium system Co(C₅H₄BF₂)₂(μ-OH) reported by Herberich and co-workers, with the B–O bond distances being comparable for the two adducts [1.569(2)/1.563(2) vs. 1.521(3)/1.556(3) Å, respectively].²⁷

Scheme 5 Reaction of P^tBu₃/2 with water.²⁴

Fig. 6 Molecular structure of [HP^tBu₃][1,1′-fc{B(C₆F₅)₂}₂(μ-OH)], [HP^tBu₃][2·(μ-OH)], with thermal ellipsoids set at the 35% probability level; hydrogen atoms (except those originating from H₂O) and solvate molecules omitted for clarity. Selected bond lengths (Å) and angles (°): B(7)–O(8) 1.569(2), B(9)–O(8) 1.563(2), B(7)–C(3) 1.596(2), B(7)–C(37/48) 1.660(2)/1.664(2), B(9)–C(10)1.593(2), B(9)–C(15/26) 1.652(2)/1.662(2), B(7)–O(8)–B(9) 139.9(1), C(3)–B(7)–C(37) 109.1(1), C(3)–B(7)–C(48) 116.2(1), C(37)–B(7)–C(48) 105.7(1), C(10)–B(9)–C(15) 109.4(1), C(10)–B(9)–C(26) 114.7(1), C(15)–B(9)–C(26) 107.4(1).

Given the vast disparity in the pK_as of H₂O and [HP^tBu₃]⁺ (ca. 31.2 and 11.4, respectively in DMSO)^28,29 the cleavage of water by P^tBu₃/2, presumably relies very heavily from a thermodynamic viewpoint on the role of 2 as a chelating Lewis acid to sequester OH⁻. With this in mind, we were also interested in examining the behaviour of this FLP in the presence of ammonia (pK_aca. 41 in DMSO),²⁸ hypothesizing that a similar mode of binding might be possible with NH₂⁻. Thus, a ‘free-pump-thaw’ degassed solution of P^tBu₃/2 was exposed to NH₃ (at 1 atm pressure) and stirred for 4 hours. The resulting yellow crystalline product was crystallized from a concentrated diethyl ether solution. However, the isolated material does not give rise to any ³¹P NMR signals, and in situ measurements of the reaction mixture show a single peak at δ_P = 61.9 corresponding to free P^tBu₃. The ¹¹B NMR spectrum of the isolated product shows a single sharp resonance at δ_B = −8.7 ppm, and the ¹⁹F NMR spectrum shows three signals at δ_F = −133.3, −156.2 and −162.7 ppm (Δδ_m,p = 6.5 ppm), diagnostic of a binding event occurring at both borane centres. The ¹H NMR signal corresponding to the NH unit integrates for six protons, suggesting formation of the bis-ammonia adduct, 1,1′-fc{B(C₆F₅)₂·NH₃}₂ [i.e.2·(NH₃)₂]. In order to confirm the formation of this adduct structurally, a higher yielding synthesis was developed via condensation of liquid ammonia onto solid 2. An immediate colour change was observed from deep purple to pale yellow, and (after venting the excess ammonia) crystals suitable for X-ray crystallography could be grown from diethyl ether solution. The structure so obtained (Fig. 3) confirms the formation of 2·(NH₃)₂. Geometrically the structure has much in common with that of 2·(IMes)₂ (also Fig. 3), with the slightly less pyramidalized nature of the BC₃ fragments [∑(∠C–B–C) = 336.7° (mean) cf. 330.0° (mean) for 2·(IMes)₂] presumably reflecting the differing donor capabilities of ammonia and IMes.

Clearly this phosphine-based FLP system does not have sufficient unquenched reactivity to deprotonate ammonia. On the other hand, NHCs have been shown to be basic enough to deprotonate the adduct H₃N·B(C₆F₅)₃.³⁰ Imidazolylidene donors form (unreactive) classical donor/acceptor adducts with 2, but the combination with the bulkier expanded ring NHC 6Dipp constitutes an FLP. Attempts were therefore made to activate ammonia using the 6Dipp/2 system: however, these also resulted in the isolation of 2·(NH₃)₂. Presumably the 2 : 1 adduct is formed very rapidly, and essentially irreversibly, on exposure of the FLP to ammonia; in the absence of the possibility for chelation (due to ‘blocking’ of the second Lewis acid function by NH₃), 6Dipp is not sufficiently basic to deprotonate the bound NH₃. Given that ItBu will deprotonate H₃N·B(C₆F₅)₃,³⁰ and that expanded ring NHCs are typically more basic than their imidazolylidene counterparts,³¹ this observation again reflects the weaker intrinsic Lewis acidity of the individual boron centres in 2 compared to B(C₆F₅)₃.^12a

FLP systems featuring 1 as the Lewis acid component are not able to bind/activate CO₂ (in contrast to P^tBu₃/B(C₆F₅)₃, for example).³¹ With this in mind, analogous FLPs containing 2 were targeted, it being not only a stronger Lewis acid, but also bifunctional, and hence potentially complementary to the Lewis basic component formed in the reaction of a phosphine/NHC with CO₂ (Fig. 5). However, benzene solutions containing either the P^tBu₃/2 or tetramethylpiperidine/2 FLP, show no propensity to bind CO₂, either at room temperature or 350 K. Both tertiary phosphines and secondary amines have previously been shown to be capable of binding CO₂ in conjunction with B(C₆F₅)₃, and the failure of systems containing 2 to act in a similar manner presumably also reflects its weaker Lewis acidity.³²

The 6Dipp/2 FLP features the strongest Lewis base under investigation, and it was postulated that this system might therefore be capable of binding CO₂. In our hands, however, we find that this reaction does not proceed cleanly, and when using benzene as the solvent, significant precipitate is formed. In previous examples of CO₂ capture by NHC-containing FLPs, an initial activation step is observed involving nucleophilic attack by the carbene at the carbon atom of CO₂, before trapping of the resulting betaine derivative by the Lewis acid component.^32c The reaction of 6Dipp with CO₂ was therefore investigated in the absence of2 in an attempt to shed light on the course of the reaction. Exposure of a benzene solution of 6Dipp to CO₂ (at ca. 1 atm pressure), results in immediate formation of an off-white precipitate. Moreover, investigation of this material by ¹H NMR (in bromobenzene-d₅), reveals signals characteristic of the formamidinium cation [(6Dipp)H]⁺, together with three multiplet resonances at 6.15, 5.14 and 5.10 ppm (integrating to 1H each), corresponding to the alkenic protons of an RCH=CH₂ unit. These observations are consistent with ring opening of the 6Dipp heterocycle via deprotonation at the C5 position (Scheme 6), in a manner analogous to that observed previously for 6Dipp in the presence of other electrophiles (e.g. H⁺, [LAu]⁺).³³ Although the product in this case could not be crystallographically characterized, peak envelopes at m/z = 405 and 447 in the positive and negative ESI-MS spectra, respectively, are consistent with the formation of the proposed cationic and anionic components.

Scheme 6 Ring opening of 6Dipp in the presence of CO₂.

In the absence of clean reactivity leading to the trapping of carbon dioxide by FLPs containing 2, attention was turned to more reactive CO₂ surrogates, such as isocyanates. The reaction of P^tBu₃/2 with CyNCO gives a complex mixture of products, and so to simplify matters, the analogous chemistry employing monofunctional 1 was probed. However, as in the case of the P^tBu₃/2 system, the ³¹P NMR spectrum measured in situ implies no net involvement of the phosphine, with an unshifted resonance being observed at δ_P = 61.9 ppm. A control reaction (without P^tBu₃) generates the same product (albeit more slowly), which gives rise to signals in the ¹¹B and ¹⁹F NMR spectra consistent with the formation of a four-coordinate boron centre. In addition, a peak envelope centred at m/z = 780 in the ESI-MS spectrum is consistent with the assimilation of two molecules of CyNCO (Scheme 7). Crystals of the product, 4, were obtained by slow cooling of a solution in benzene-d₆, and X-ray crystallography was used to unambiguously determine the connectivity associated with insertion of two molecules of CyNCO into the C_Cp–B bond of 1 (Fig. 7).

Scheme 7 Reaction of CyNCO with the P^tBu₃/1 FLP (or with 1 alone), leading to the formation of 4.

Fig. 7 Molecular structure of 4, with thermal ellipsoids set at the 35% probability level; hydrogen atoms and solvate molecules omitted, and cyclohexyl groups shown in wireframe format for clarity. Selected bond lengths (Å): C(9)–C(12) 1.452(2), C(12)–O(13) 1.288(2), O(13)–B(14) 1.534(2), B(14)–N(15) 1.533(3), N(15)–C(16) 1.332(3), C(16)–N(17) 1.475(2), C(12)–N(17) 1.340(3), C(16)–O(24) 1.215(3).

The molecular structure is based around a non-planar six-membered CNCNBO heterocycle featuring a pendant carbonyl function. Analysis of the bond lengths within the heterocycle suggest that there is some degree of delocalized π character within the O(13)–C(12)–N(17) unit [d{C(12)–O(13)} = 1.288(2) Å] and also within the amido function defined by N(15)–C(16)–O(24) [d{N(15)–C(16)} = 1.332(3) Å]. The relatively long C(16)–N(17) distance [1.475(2) Å], on the other hand, suggests less significant delocalization between these two fragments.

The insertion of heterocumulenes of this sort into reactive B–C bonds is by no means unprecedented. Cowley and co-workers have reported the insertion of dicyclohexyl carbodiimide into the B–C bond of PhBCl₂ to give the benzamidinate system {PhC(CyN)₂}BCl₂ (Scheme 8a),^34,35 and a similar initial step in the reaction of 1 with CyNCO would generate a closely-related BNCO four-membered ring via migration of the more nucleophilic ferrocenyl fragment (cf. C₆F₅; Scheme 8b). The more electrophilic nature of the boron centre in this intermediate then presumably facilitates nucleophilic attack by a second equivalent of the isocyanate, with subsequent ring-closure generating the observed 6-membered heterocyclic product.

Scheme 8 (a) Mechanism for the insertion of a carbodiimide into the B–C bond of PhBCl₂ as reported by Cowley and co-workers;³⁴ (b) potential mechanism for the double insertion of cyclohexyl isocyanate into the B–C_Cp bond of 1 to give 4.

Experimental

Caution: Solutions containing LiC₆F₅ are known to explode at temperatures in excess of −40 °C.

General considerations

All manipulations were carried out using standard Schlenk line or dry-box techniques under an atmosphere of argon or dinitrogen, respectively. Solvents were degassed by sparging with argon and dried by passing through a column of the appropriate drying agent using a commercially available Braun SPS. NMR spectra were recorded in chloroform-d, benzene-d₆, bromobenzene-d₅ or THF-d₈, which were dried over molecular sieves, potassium, calcium hydride or calcium hydride respectively, and stored under argon in Teflon valve ampoules. NMR samples were prepared under argon in 5 mm Wilmad 507-PP tubes fitted with J. Young Teflon valves. ¹H and ¹³C NMR spectra were recorded on Varian Mercury-VX-300 or Bruker AVII-500 spectrometers and referenced internally to residual protio-solvent (¹H) or solvent (¹³C) resonances and are reported relative to tetramethylsilane (δ = 0 ppm). ¹¹B, ¹⁹F and ³¹P NMR spectra were referenced with respect to Et₂O·BF₃, CFCl₃ and 85% aqueous H₃PO₄, respectively. Chemical shifts are quoted in δ (ppm) and coupling constants in Hz. UV-vis spectra were collected on a Scintio UV S-2100 UV/Vis spectrometer. Elemental analyses were carried out at London Metropolitan University. BrC₆F₅, ⁿBuLi, P^tBu₃, PPh₃, lutidine, tetramethylpiperidine, ammonia and carbon dioxide were sourced commercially. 1,1′-fc(BBr₂)₂, FcB(C₆F₅)₂ (1), and NHCs (IMes, IDipp, IMesCl₂, 6Mes and 6Dipp) were prepared by literature routes.^14,15,36

Syntheses of novel compounds

1,1′-fc{B(C₆F₅)₂}₂ (2). To a solution of bromopentafluorobenzene (5.89 mL, 47.5 mmol) in hexane (30 mL) at −78 °C, was added dropwise ⁿBuLi (29.7 mL of a 1.6 M solution, 47.5 mmol) and the mixture stirred at −78 °C for 45 min. Caution: LiC₆F₅ is known to explode at temperatures above −40 °C. A solution of 1,1′-fc(BBr₂)₂ (6.10 g, 11.6 mmol) also in hexane (150 mL), was then added dropwise at −78 °C, and the resulting mixture allowed to warm slowly to room temperature over a period of 12 h. After removal of volatiles in vacuo the product was extracted into hot hexane. Further removal of the volatiles in vacuo, and washing of the resulting solid with pentane, yielded a dark purple solid which was dried thoroughly, and found to be of sufficient purity for subsequent chemistry without further recrystallization. Yield: 5.45 g, 54%. ¹H, ¹¹B and ¹⁹F NMR data agree with literature values.^12b

General procedure for investigating the formation of Lewis base adducts of 2

The procedure is exemplified for the case of IMes in a 2 : 1 molar ratio. This and other Lewis bases were probed in both 2 : 1 and 1 : 1 molar ratios. In the case of 1,1′-fc{B(C₆F₅)₂·IMes}₂, 2·(IMes)₂, the product was isolated and characterized by standard spectroscopic, analytical and crystallographic methods. For other Lewis bases, in situ¹¹B and ¹⁹F NMR data (based on those measured for 2·(IMes)₂) were used to determine whether or not a classical Lewis acid/base adduct was formed. IMes (0.035 g, 0.116 mmol) and 2 (0.100 g, 0.058 mmol) were dissolved in the minimum benzene required to dissolve all solid material (ca. 5 mL), and the reaction mixture stirred for 24 h at room temperature. Volatiles were then removed in vacuo, and the product recrystallized from THF/hexane as single crystals suitable for X-ray crystallography. Yield: 0.056 g, 65%.

Characterizing data for 2·(IMes)₂

¹H NMR (500 MHz, THF-d₈, 20 °C): δ 7.59, 7.46 (d, ²J_H–H = 2.1 Hz, each 2H, backbone CH of IMes), 6.99, 6.90, 6.70, 6.45 (s, each 2H, IMes aromatic CH), 3.80, 3.55, 3.22, 2.77 (br s, each 2H, CH of Cp), 2.40, 2.24, 2.20, 2.18, 1.98, 1.81 (s, each 6H, Me of IMes). ¹¹B NMR (128 MHz, THF-d₈, 20 °C): δ −14 (sharp). ¹⁹F NMR (377 MHz, THF-d₈, 20 °C): δ −117.8 (d, ³J_FF = 24.5 Hz, ortho-CF of C₆F₅), −119.0 (d, ³J_FF = 24.5 Hz, ortho-CF of C₆F₅), −123.9 (d, ³J_FF = 24.5 Hz, ortho-CF of C₆F₅), −128.1 (d, ³J_FF = 24.5 Hz, ortho-CF of C₆F₅), −163.3 (t, ³J_FF = 19.5 Hz, para-CF of C₆F₅), −164.1 (t, ³J_FF = 20.0 Hz, para-CF of C₆F₅), −167.1 (t, ³J_FF = 22.1 Hz, meta-CF of C₆F₅), −167.4 (t, ³J_FF = 22.1 Hz, meta-CF of C₆F₅), −167.9 (t, ³J_FF = 22.1 Hz, meta-CF of C₆F₅), −168.6 (t, ³J_FF = 22.1 Hz, meta-CF of C₆F₅). Elemental microanalysis: calc. (for C₇₆H₅₆B₂F₂₀FeN₄) C 61.53, H 3.81, N 3.78; meas. C 61.88, H 4.01, N 3.66. Crystallographic data: 2·(IMes)₂·3/2(THF)·3/2(pentane), C₈₈H₈₃B₂F₂₀FeN₄O_1.5, M_r = 1678.05, orthorhombic, P 2ac 2ab, a = 11.4405(1), b = 22.3759(2), c = 32.0362(2) Å, V = 8201.0(1) ų, Z = 4, ρ_c = 1.359 Mg m⁻³, T = 150 K, λ = 1.54180 Å. 17 080 reflections collected, 16 778 independent [R(int) = 0.029] used in all calculations. R₁ = 0.0421, wR₂ = 0.1252 for observed unique reflections [I > 2σ(I)] and R₁ = 0.0428, wR₂ = 0.1263 for all unique reflections. Max. and min. residual electron densities 0.84 and −0.49 e ų. CCDC reference: 1582718.†

In situ NMR data for 2·(IMesCl₂)₂

¹¹B NMR (128 MHz, benzene, 20 °C): δ −13 (sharp). ¹⁹F NMR (377 MHz, benzene, 20 °C): δ −117.0 (d, ³J_FF = 16.0 Hz, ortho-CF of C₆F₅), −118.9 (d, ³J_FF = 16.0 Hz, ortho-CF of C₆F₅), −122.3 (d, ³J_FF = 16.0 Hz, ortho-CF of C₆F₅), −128.5 (d, ³J_FF = 16.0 Hz, ortho-CF of C₆F₅), −159.3 (d, ³J_FF = 22.5 Hz, para-CF of C₆F₅), −162.0 (d, ³J_FF = 22.5 Hz, para-CF of C₆F₅), −164.3 (d, ³J_FF = 20.9 Hz, meta-CF of C₆F₅), −165.4 (d, ³J_FF = 20.9 Hz, meta-CF of C₆F₅), −166.3 (d, ³J_FF = 20.9 Hz, meta-CF of C₆F₅), −166.5 (d, ³J_FF = 20.9 Hz, meta-CF of C₆F₅).

In situ NMR data for 2·(6Mes)₂

¹¹B NMR (128 MHz, benzene, 20 °C): δ −11 (sharp). ¹⁹F NMR (377 MHz, benzene, 20 °C): δ −112.6 (d, ³J_FF = 29.7 Hz, ortho-CF of C₆F₅), −118.8 (d, ³J_FF = 27.4 Hz, ortho-CF of C₆F₅), −119.9 (d, ³J_FF = 24.5 Hz, ortho-CF of C₆F₅), −123.0 (d, ³J_FF = 25.4 Hz, ortho-CF of C₆F₅), −153.3 (t, ³J_FF = 19.4 Hz, para-CF of C₆F₅), −158.3 (t, ³J_FF = 19.4 Hz, para-CF of C₆F₅), −161.2 (t, ³J_FF = 21.3 Hz, meta-CF of C₆F₅), −163.6 (t, ³J_FF = 23.6 Hz, meta-CF of C₆F₅), −164.2 (t, ³J_FF = 23.9 Hz, meta-CF of C₆F₅), −165.6 (t, ³J_FF = 21.4 Hz, meta-CF of C₆F₅).

In situ NMR data for 2·(PⁿBu₃)₂

¹¹B NMR (128 MHz, benzene, 20 °C): δ −11 (broad). ¹⁹F NMR (377 MHz, benzene, 20 °C): δ −126.2 (broad s, ortho-CF of C₆F₅), −157.9 (t, ³J_FF = 20.3 Hz, para-CF of C₆F₅), −163.7 (t, ³J_FF = 20.3 Hz, meta-CF of C₆F₅). ³¹P NMR (162 MHz, benzene, 20 °C): δ −2.9.

In situ NMR data from the reaction of 2 with PCy₃

(500 MHz, chloroform-d, 20 °C): δ 4.42, 4.38, 4.22, 4.09, 3.65, 3.29, 3.11, 3.08 (broad s, each 1H, C₅H₄B), 2.65 (m, 3H, Cy), 2.10–1.22 (overlapping m, 30 H, Cy). ¹¹B NMR (128 MHz, benzene-d₆, 20 °C): δ 32 (very broad), 3 (broad). ¹⁹F NMR (377 MHz, benzene-d₆, 20 °C): δ −123.4 (s, 2F, C₆F₄), −129.3 (s, orthoCF of B(C₆F₅)₂), −123.0 (s, orthoCF of B(C₆F₅)₂), −131.4 (s, 2F, C₆F₄), −131.9 (s, orthoCF of BF(C₆F₄PCy₃)(C₆F₅)), −156.3 (broad s, paraCF of B(C₆F₅)₂), −156.7 (broad s, paraCF of B(C₆F₅)₂), −160.1 (s, paraCF of BF(C₆F₄PCy₃)(C₆F₅)), −163.5 (s, metaCF of B(C₆F₅)₂), −163.9 (s, metaCF of B(C₆F₅)₂), −164.5 (s, metaCF of BF(C₆F₄PCy₃)(C₆F₅)), −194.9 (s, BF). ³¹P NMR (162 MHz, benzene-d₆, 20 °C): δ 40.1.

3 . A mixture of PCy₃ (0.053 g, 0.19 mmol) and 1 (0.100 g, 0.19 mmol) were dissolved in benzene-d₆ (2 mL) at which point analysis by ¹H, ¹¹B and ³¹P NMR spectroscopy revealed an unquenched mixture of Lewis acid and Lewis base components. After stirring for 10 d, a brown oil formed at the bottom of the reaction vessel; volatiles were removed in vacuo, and the resulting residue dissolved in chloroform-d (5 mL) and layered with hexane. A very small quantity of orange crystals was formed, which was isolated by filtration and dried in vacuo. Yield: <5%. ¹H NMR (500 MHz, chloroform-d, 20 °C): δ 4.42 (broad s, 2H, C₅H₄B), 4.18 (broad s, 5H, Cp), 3.35 (broad s, 2H, C₅H₄B), 2.90 (m, 3H, PCH of Cy), 2.13–1.27 (overlapping m, 30 H, CH₂ of Cy). ¹¹B NMR (96 MHz, chloroform-d, 20 °C): δ 2 (broad). ¹⁹F NMR (282 MHz, chloroform-d, 20 °C): δ −124.7 (m, 2F, C₆F₄), −132.0 (m, 2F, C₆F₄), −133.3 (d, ³J_FF = 20.9 Hz, ortho-CF of C₆F₅), −162.2 (t, ³J_FF = 20.9 Hz, para-CF of, C₆F₅), −165.8 (m, meta-CF of C₆F₅), −193.7 (broad s, BF). ³¹P NMR (121 MHz, chloroform-d, 20 °C): δ 39.9. Crystallographic data: 3·CHCl₃, C₄₁H₄₃BCl₃F₁₀FeP, M_r = 929.76, triclinic, P1̄, a = 11.7155(3), b = 12.6410(4), c = 15.6649(3) Å, α = 83.830(2), β = 79.824(2), γ = 66.833(3)°, V = 2097.4(1) ų, Z = 2, ρ_c = 1.472 Mg m⁻³, T = 150 K, λ = 1.54180 Å. 8635 reflections collected, 8635 independent [R(int) = 0.019] used in all calculations. R₁ = 0.0357, wR₂ = 0.0824 for observed unique reflections [I > 2σ(I)] and R₁ = 0.0374, wR₂ = 0.0838 for all unique reflections. Max. and min. residual electron densities 0.54 and −0.51 e ų. CCDC reference: 954137.†

[HP^tBu₃][2·(μ-OH)]. 2 (0.100 g, 0.114 mmol) was dissolved in minimal benzene and combined with P^tBu₃ (0.023 g, 0.114 mmol). One drop of deionized water was added and the mixture stirred for 1 h. Volatiles were removed in vacuo and single crystals of the product obtained from a concentrated chloroform solution stored at −30 °C. Yield: 0.097 g, 78%. ¹H NMR (500 MHz, chloroform-d, 20 °C): δ 5.46 (broad s, 1H, OH), 4.06 (d, ¹J_PH = 461 Hz, 1H, PH), 3.91 (s, 4H, Cp), 3.68 (s, 4H, Cp), 1.55 (d, ³J_PH = 15.2 Hz, 27H, ^tBu). ¹¹B NMR (128 MHz, chloroform-d, 20 °C): δ 1 (broad). ¹⁹F NMR (377 MHz, chloroform-d, 20 °C): δ −132.4 (d, ³J_FF = 10.7 Hz, ortho-CF of C₆F₅), −160.4 (t, ³J_FF = 20.4 Hz, para-CF of C₆F₅), −164.8 (t, ³J_FF = 19.5 Hz, meta-CF of C₆F₅). ³¹P NMR (121 MHz, chloroform-d, 20 °C): δ 58.3. ESI-MS (m/z): (pos) 203.2 [HP^tBu₃]⁺; (neg) 921.0 [2·(μ-OH)]⁻. Elemental microanalysis: calc. (for C₅₅H₄₆B₂F₂₀FeOP) C 54.49, H 3.83%; meas. C 54.88, H 4.01%. Crystallographic data: [HP^tBu₃][2·(μ-OH)]·3/2(benzene), C₅₅H₄₆B₂F₂₀FeOP, M_r = 1211.37, triclinic, P1̄, a = 11.8245(4), b = 13.6477(4), c = 15.8558(4) Å, α = 84.214(2), β = 88.541(2), γ = 87.111(3)°, V = 2542.0(1) ų, Z = 2, ρ_c = 1.583 Mg m⁻³, T = 150 K, λ = 1.54180 Å. 27 110 reflections collected, 10 487 independent [R(int) = 0.026] used in all calculations. R₁ = 0.0326, wR₂ = 0.804 for observed unique reflections [I > 2σ(I)] and R₁ = 0.0351, wR₂ = 0.0822 for all unique reflections. Max. and min. residual electron densities 0.31 and −0.39 e ų. CCDC reference: 1576950.†

2·(NH₃)₂. A Schlenk flask containing 2 (0.100 g, 0.114 mmol) was cooled to −60 °C and sufficient NH₃ condensed to allow all of the solid material to dissolve. The solution was stirred, and allowed to warm to 20 °C, while ammonia gas was vented to waste. The resulting yellow solid was isolated, and single crystals suitable for X-ray crystallography were obtained from a concentrated ether solution stored at −30 °C. Yield: 0.089 g, 86%. ¹H NMR (500 MHz, benzene-d₆, 20 °C): δ 3.89 (s, 4H, C₅H₄), 3.55 (s, 4H, C₅H₄) 3.41 (b s, 6H, NH). ¹⁹F NMR (377 MHz, benzene-d₆, 20 °C): δ −133.3 (d, ³J_FF = 9.2 Hz, ortho-CF of C₆F₅), −156.2 (t, ³J_FF = 20.4 Hz, para-CF of C₆F₅), −162.7 (t, ³J_FF = 22.4 Hz, meta-CF of C₆F₅). ¹¹B NMR (128 MHz, benzene-d₆, 20 °C): −9 (sharp). Elemental microanalysis: calc. (for C₃₄H₁₄B₂F₂₀FeN₂) C 44.94, H 1.55, N 3.08%; meas. C 44.89, H 1.56, N 3.28%. MS (ESI): 908.1. Crystallographic data: 2·(NH₃)₂·3/2(C₆H₆), C₄₃H₂₃B₂F₂₀FeN₂, M_r = 1025.10, triclinic, P1̄, a = 10.4515(3), b = 13.5721(3), c = 14.2616(4) Å, α = 94.087(2), β = 93.027(3), γ = 100.948(2)°, V = 1976.6(1) ų, Z = 2, ρ_c = 1.722 Mg m⁻³, T = 150 K, λ = 1.54180 Å. 41 166 reflections collected, 8188 independent [R(int) = 0.021] used in all calculations. R₁ = 0.0259, wR₂ = 0.0656 for observed unique reflections [I > 2σ(I)] and R₁ = 0.0270, wR₂ = 0.0664 for all unique reflections. Max. and min. residual electron densities 0.32 and −0.34 e ų. CCDC reference: 1576951.†

Reaction of 6Dipp with CO₂. 6-Dipp (0.100 g, 0.247 mmol) was dissolved in minimal benzene, the solution freeze–pump–thaw degassed, and the evacuated headspace backfilled with CO₂ to 1 bar pressure. The reaction mixture was stirred for 4 h, and the resulting precipitate then isolated by filtration, washed with pentane and dried in vacuo. The product was dissolved in 0.6 mL of bromobenzene-d₅ and transferred to a J. Young's tube for analysis by multinuclear NMR. ¹H NMR (500 MHz, bromobenzene-d₅, 20 °C): (signals due to cation) δ 7.19 (m, 6H, aromatic CH of Dipp), 3.61 (m, 4H, NCH₂), 3.10 (sept, ³J_HH = 7.1 Hz, 4H, CH of ⁱPr), 2.39 (m, 2H, CH₂), 1.38 (d, ³J_HH = 7.1 Hz, 24H, Me of ⁱPr); (signals due to anion) 7.19 (m, 6H, Ar), 6.15 (m, 1H, alkene CH), 5.14 (m, 1H, alkene CH₂), 5.10 (broad s, 1H, alkene CH₂), 4.35 (d, ³J_HH = 6.5 Hz, 2H, CH₂), 3.10 (m, 4H, CH of ⁱPr), 1.24 (d, 24H, Me of ⁱPr). ESI-MS (m/z): (pos) 405 [6-DippH]⁺; (neg) 447 [C₂₉H₃₉N₂O₂]⁻.

4 . 1 (0.100 g, 0.189 mmol) and excess (>5 equiv.) of CyNCO were dissolved in benzene-d₆ and the resulting solution transferred to a Young's NMR tube, for spectroscopic analysis over a period of one week. Storage at 6 °C resulted in the formation of orange-red crystals. ¹H NMR (500 MHz, chloroform-d, 20 °C): δ 4.89 (t, ³J_HH = 2.1 Hz, 2H, Cp), 4.80 (t, ³J_HH = 2.1 Hz, 2H, Cp), 4.18 (s, 5H, Cp), 4.02 (tt, ³J_HH = 12.0 Hz, ⁴J_HH = 3.4 Hz, 1H, CH of Cy), 3.04 (tt, ³J_HH = 12.0 Hz, ⁴J_HH = 3.4 Hz, 1H, CH of Cy), 2.70–1.05 (20H, CH₂ of Cy). ¹⁹F NMR (282 MHz, chloroform-d, 20 °C): δ −133.2 (d, ³J_FF = 25.2 Hz, ortho-CF of C₆F₅), −156.0 (t, ³J_FF = 20.9 Hz, para-CF of C₆F₅), −163.1 (td, ³J_FF = 21.9 Hz, ⁴J_FF = 9.6 Hz, meta-CF of C₆F₅). ¹¹B NMR (96 MHz, chloroform-d, 20 °C): δ 1. ¹³C NMR (126 MHz, chloroform-d, 20 °C): 178.1 (CO), 149.4 (Fc quaternary C), 148.1 (d, ¹J_CF = 243.5 Hz, C₆F₅), 140.3 (d, ¹J_CF = 254.2 Hz, C₆F₅), 137.0 (d, ¹J_CF = 255.6 Hz, C₆F₅), 75.0 (C₅H₄), 72.8 (C₅H₄), 70.7 (Cp), 61.8 (CH of Cy), 50.0 (CH of Cy), 31.2, 30.1, 28.9, 27.9, 26.5, 24.9 (CH₂ of Cy). ESI-MS (m/z): (pos) 780 [M]⁺; accurate mass: calc. (for C₃₆H₃₁BF₁₀FeN₂O₂, [M]⁺) 781.1747; meas. 781.1748. Crystallographic data: 4·C₆H₆, C₄₂H₃₇BF₁₀FeN₂O₂, M_r = 858.41, triclinic, P1̄, a = 10.9221(1), b = 11.1191(1), c = 17.0196(2) Å, α = 94.976(1), β = 95.697(1), γ = 112.976(1)°, V = 1875.7(1) ų, Z = 2, ρ_c = 1.520 Mg m⁻³, T = 150 K, λ = 1.54180 Å. 55 367 reflections collected, 8562 independent [R(int) = 0.030] used in all calculations. R₁ = 0.0389, wR₂ = 0.0842 for observed unique reflections [I > 2σ(I)] and R₁ = 0.0648, wR₂ = 0.0926 for all unique reflections. Max. and min. residual electron densities 0.67 and −0.57 e ų. CCDC reference: 1576592.†

Crystallography

Data for 2·(IMes)₂, [HP^tBu₃][2·(μ-OH)], 2·(NH₃)₂, 3 and 4 were collected on a Oxford Diffraction Supernova diffractometer at 150 K. Data collection and reduction were carried out using CrysAlisPro or Denzo/Scalepack, structure solution using Superflip, and refinement using CRYSTALS or SHELXT-2014/7.³⁷ Complete details of all structures are contained within the respective CIFs which have been deposited with the CCDC (reference numbers: 954137, 1576950–1576952 and 1582718).†

Conclusions

The bifunctional Lewis acid 1,1′-fc{B(C₆F₅)₂}₂ (2) is shown to form frustrated Lewis pairs with the sterically encumbered N-donor bases lutidine and tetramethylpiperidine, together with PPh₃, P^tBu₃ and the expanded ring carbene 6Dipp. In the case of PCy₃, attack at the para-CF bond of one of the C₆F₅ groups leads to nucleophilic aromatic substitution with accompanying migration of fluoride to boron. The more facile nature of this chemistry in comparison to that observed for the mono-functional analogue FcB(C₆F₅)₂ (1) can be attributed to the more electron deficient nature of the -B(C₆F₅)₂ functions in 2.

The P^tBu₃/2 FLP can be shown to cleave one of the O–H bonds in water to give a tertiary phosphonium salt in which the anion features a symmetrically bound ‘inverse-chelated’ B–O(H)–B unit. Attempts to bring about analogous N–H bond activation with ammonia are frustrated by the weaker Brønsted acidity of the N–H bond and/or the inability to generate a similar B–N(H)₂–B motif due to the (less reversible) formation of strong H₃N→B donor/acceptor bonds. Neither P^tBu₃/1 or P^tBu₃/2 shows any propensity to activate carbon dioxide, in contrast to the combination of P^tBu₃ and the stronger Lewis acid B(C₆F₅)₃. Attempts to use the stronger Lewis base 6Dipp lead to ring opening of the carbene brought about by coordination to the electrophilic C-atom of CO₂, while the use of the more reactive heterocumulene CyNCO can be shown to lead to insertion into the C–B bond linking the borane function to the ferrocene backbone.

Conflicts of interest

There are no conflicts to declare.

Acknowledgements

We acknowledge funding from the EPSRC (studentship to MJK: EP/P505216/1), and Dr Jamie Hicks (Oxford) for help with crystallography.

Notes and references

1. Initial identification of steric frustration in Lewis acid/base complex formation: H. C. Brown, H. I. Schlesinger and S. Z. Cardon, J. Am. Chem. Soc., 1942, 64, 325.
2. Initial demonstration of the use of FLPs in small molecule activation: G. C. Welch, R. R. S. Juan, J. D. Masuda and D. W. Stephan, Science, 2006, 314, 1124.
3. For a recent review, see: D. W. Stephan and G. Erker, Angew. Chem., Int. Ed., 2015, 54, 6400.
4. See, for example: T. J. Herrington, A. J. W. Thom, A. J. P. White and A. E. Ashley, Dalton Trans., 2012, 41, 9019.
5. See, for example: C. Appelt, J. C. Slootweg, K. Lammertsma and W. Uhl, Angew. Chem., Int. Ed., 2013, 52, 4256.
6. See, for example: J. M. Farrell, J. A. Hatnean and D. W. Stephan, J. Am. Chem. Soc., 2012, 134, 15728.
7. See, for example: A. M. Chapman, M. F. Haddow and D. F. Wass, J. Am. Chem. Soc., 2011, 133, 18463.
8. C. R. Wade, A. E. J. Broomsgrove, S. Aldridge and F. P. Gabbaï, Chem. Rev., 2010, 110, 3958.
9. (a) C. Dusemund, K. R. A. S. Sandanayake and S. Shinkai, J. Chem. Soc., Chem. Commun., 1995, 333; (b) H. Yamamoto, A. Ori, K. Ueda, C. Dusemund and S. Shinkai, Chem. Commun., 1996, 407; (c) C. Bresner, S. Aldridge, I. A. Fallis, C. Jones and L.-L. Ooi, Angew. Chem., Int. Ed., 2005, 44, 3606; (d) K. Venkatasubbaiah, L. N. Zakharov, W. S. Kassel, A. L. Rheingold and F. Jäkle, Angew. Chem., Int. Ed., 2005, 44, 5428; (e) C. Bresner, J. K. Day, N. D. Coombs, I. A. Fallis, S. Aldridge, S. J. Coles and M. B. Hursthouse, Dalton Trans., 2006, 3660; (f) J. K. Day, C. Bresner, I. A. Fallis, L.-L. Ooi, D. J. Watkin, S. J. Coles, L. Male, M. B. Hursthouse and S. Aldridge, Dalton Trans., 2007, 3486; (g) K. Venkatasubbaiah, I. Nowik, R. H. Herber and F. Jäkle, Chem. Commun., 2007, 2154; (h) J. K. Day, C. Bresner, N. D. Coombs, I. A. Fallis, L.-L. Ooi and S. Aldridge, Inorg. Chem., 2008, 47, 793; (i) A. E. J. Broomsgrove, D. Addy, C. Bresner, I. A. Fallis, A. L. Thompson and S. Aldridge, Chem. – Eur. J., 2008, 14, 7525; (j) T. Pakkirisamy, K. Venkatasubbaiah, W. S. Kassel, A. L. Rheingold and F. Jäkle, Organometallics, 2008, 27, 3056; (k) K. Venkatasubbaiah, T. Pakkirisamy, R. A. Lalancette and F. Jäkle, Dalton Trans., 2008, 4507; (l) I. R. Morgan, A. Di Paolo, D. Vidovic, I. A. Fallis and S. Aldridge, Chem. Commun., 2009, 7288; (m) A. E. J. Broomsgrove, D. Addy, A. Di Paolo, I. R. Morgan, C. Bresner, V. Chislett, I. A. Fallis, A. L. Thompson, D. Vidovic and S. Aldridge, Inorg. Chem., 2010, 49, 157; (n) C. Bresner, C. J. E. Haynes, D. A. Addy, A. E. J. Broomsgrove, P. Fitzpatrick, D. Vidovic, A. L. Thompson, I. A. Fallis and S. Aldridge, New J. Chem., 2010, 34, 1652; (o) I. R. Morgan, A. E. J. Broomsgrove, P. Fitzpatrick, D. Vidovic, A. L. Thompson, I. A. Fallis and S. Aldridge, Organometallics, 2010, 29, 4762; (p) I. Siewert, P. Fitzpatrick, A. E. J. Broomsgrove, M. Kelly, D. Vidovic and S. Aldridge, Dalton Trans., 2011, 40, 10345; (q) I. Siewert, D. Vidovic and S. Aldridge, J. Organomet. Chem., 2011, 696, 2528; (r) M. J. Kelly, A. E. J. Broomsgrove, I. R. Morgan, I. Siewert, P. Fitzpatrick, J. Smart, D. Vidovic and S. Aldridge, Organometallics, 2013, 32, 2674; (s) R. Tirfoin and S. Aldridge, Dalton Trans., 2013, 42, 12836; (t) P. Thilagar, D. Murillo, J. Chen and F. Jäkle, Dalton Trans., 2013, 42, 665; (u) R. Tirfoin, J. A. B. Abdalla and S. Aldridge, Dalton Trans., 2015, 44, 13049; (v) R. Tirfoin, J. A. B. Abdalla and S. Aldridge, Chem. – Eur. J., 2015, 21, 11813.
10. A. Ramos, A. J. Lough and D. W. Stephan, Chem. Commun., 2009, 1118.
11. (a) M. J. Kelly, J. Gilbert, R. Tirfoin and S. Aldridge, Angew. Chem., Int. Ed., 2013, 52, 14094. See also: (b) Z. Mo, E. L. Kolychev, A. Rit, J. Campos, H. Niu and S. Aldridge, J. Am. Chem. Soc., 2015, 137, 12227.
12. (a) B. E. Carpenter, W. E. Piers, M. Parvez, G. P. A. Yap and S. J. Rettig, Can. J. Chem., 2001, 79, 857; (b) B. E. Carpenter, W. E. Piers and R. McDonald, Can. J. Chem., 2001, 79, 291; (c) D. J. Parks, W. E. Piers and G. P. A. Yap, Organometallics, 1998, 17, 5492.
13. E. Otten, R. C. Neu and D. W. Stephan, J. Am. Chem. Soc., 2009, 131, 9918.
14. M. J. Kelly, R. Tirfoin, J. Gilbert and S. Aldridge, J. Organomet. Chem., 2014, 769, 11.
15. B. Wrackmeyer, U. Dörfler, W. Milius and M. Herberhold, Z. Naturforsch., B: J. Chem. Sci., 1996, 51, 851.
16. P. L. Coe, R. Stephens and J. C. Tatlow, J. Chem. Soc., 1962, 3227.
17. See also: S. Kronig, E. Theuergarten, D. Holschumacher, T. Bannenberg, C. G. Daniluc, P. G. Jones and M. Tamm, Inorg. Chem., 2011, 50, 7344.
18. (a) P. deFreḿont, N. M. Scott, E. D. Stevens and S. P. Nolan, Organometallics, 2005, 24, 2411; (b) J. J. Dunsford, K. J. Cavell and B. Kariuki, Organometallics, 2012, 31, 4118.
19. %V_bur: (a) A. C. Hillier, W. J. Sommer, B. S. Yong, J. L. Petersen, L. Cavallo and S. P. Nolan, Organometallics, 2003, 22, 4322; (b) L. Cavallo, A. Correa, C. Costabile and H. Jacobsen, J. Organomet. Chem., 2005, 690, 5407; (c) A. Poater, B. Cosenza, A. Correa, S. Giudice, F. Ragone, V. Scarano and L. Cavallo, Eur. J. Inorg. Chem., 2009, 1759; (d) F. Ragone, A. Poater and L. Cavallo, J. Am. Chem. Soc., 2010, 132, 4249; (e) H. Clavier and S. P. Nolan, Chem. Commun., 2010, 46, 841.
20. G. C. Welch, R. Prieto, M. A. Dureen, A. J. Lough, O. A. Labeodan, T. Höltrichter-Rössmann and D. W. Stephan, Dalton Trans., 2009, 1559.
21. See, for example: T. Beringhelli, D. Maggioni and G. D'Alfonso, Organometallics, 2001, 20, 4927.
22. G. C. Welch, L. Cabrera, P. A. Chase, E. Hollink, J. D. Masuda, P. Wei and D. W. Stephan, Dalton Trans., 2007, 3407.
23. See also M. J. Sgro, J. Dömer and D. W. Stephan, Chem. Commun., 2012, 48, 7253.
24. (a) G. C. Welch and D. W. Stephan, J. Am. Chem. Soc., 2007, 129, 1880; (b) V. Sumerin, F. Schulz, M. Nieger, M. Leskela, T. Repo and B. Rieger, Angew. Chem., Int. Ed., 2008, 47, 6001; (c) S. J. Geier and D. W. Stephan, J. Am. Chem. Soc., 2009, 131, 3476.
25. 2 captures/cleaves H₂O over a relatively short timeframe (ca. 1 h). Prolonged exposure to excess water, however, leads to the formation of boric acid, pentafluorobenzene and ferrocene, each of which could be characterized by multinuclear NMR. Such chemistry mirrors the behaviour of 1 towards water, which also proceeds via B–C bond cleavage.^12a.
26. For an earlier example of O–H bond cleavage in water by an FLP, see: R. Roesler, W. E. Piers and M. Parvez, J. Organomet. Chem., 2003, 680, 218.
27. G. E. Herberich, U. Englert, A. Fischer and D. Wiebelhaus, Organometallics, 1998, 17, 4769.
28. http: //evans.rc.fas.harvard.edu/pdf/evans_pKa_table.pdf . Retrieved 24 September 2017.
29. M. R. Netherton and G. C. Fu, Org. Lett., 2001, 3, 4295.
30. P. A. Chase and D. W. Stephan, Angew. Chem., Int. Ed., 2008, 47, 7433.
31. A. M. Magill, K. J. Cavell and B. F. Yates, J. Am. Chem. Soc., 2004, 126, 8717.
32. (a) C. M. Mömming, E. Otten, G. Kehr, R. Fröhlich, S. Grimme, D. W. Stephan and G. Erker, Angew. Chem., Int. Ed., 2009, 48, 6643; (b) T. Voss, T. Mahdi, E. Otten, R. Fröhlich, G. Kehr, D. W. Stephan and G. Erker, Organometallics, 2012, 31, 2367; (c) E. Theuergarten, T. Bannenberg, M. D. Walter, D. Holschumacher, M. Freytag, C. G. Daniliuc, P. G. Jones and M. Tamm, Dalton Trans., 2014, 43, 1651.
33. N. Phillips, R. Tirfoin and S. Aldridge, Chem. – Eur. J., 2014, 20, 3825.
34. N. J. Hill, J. A. Moore, M. Findlater and A. H. Cowley, Chem. Commun., 2005, 5462.
35. See also: (a) G. A. Pierce, D. Vidovic, D. L. Kays, N. D. Coombs, A. L. Thompson, E. D. Jemmis, S. De and S. Aldridge, Organometallics, 2009, 28, 2947; (b) S. De, G. A. Pierce, D. Vidovic, D. L. Kays, N. D. Coombs, E. D. Jemmis and S. Aldridge, Organometallics, 2009, 28, 2961.
36. (a) IMes: A. J. Arduengo III, H. V. R. Dias, R. L. Harlow and M. Kline, J. Am. Chem. Soc., 1992, 114, 5530; (b) IMesCl₂: A. J. Arduengo III, F. Davidson, H. V. R. Dias, J. R. Goerlich, D. Khanis, W. J. Marshall and T. K. Prakasha, J. Am. Chem. Soc., 1997, 119, 12742; (c) IDipp: A. J. Arduengo IiI, R. Krafczyk, R. Schmutzler, H. A. Craig, J. R. Goerlich, W. J. Marshall and M. Unverzagt, Tetrahedron, 1999, 55, 14523; (d) 6Mes, 6Dipp: M. Iglesias, D. J. Beetstra, J. C. Knight, L. Ooi, A. Stasch, S. Coles, L. Male, M. B. Hursthouse, K. J. Cavell, A. Dervisi and I. A. Fallis, Organometallics, 2008, 27, 3279.
37. (a) Z. Otwinowski and W. Minor, in Processing of X-Ray Diffraction Data Collected in Oscillation Mode, Methods Enzymol, ed. C. W. Carter and R. M. Sweet, Academic Press, New York, 1997, pp. 307–326; (b) A. Altomare, G. Cascarano, C. Giacovazzo and A. Guagliardi, J. Appl. Crystallogr., 1993, 26, 343; (c) L. Palatinus and G. Chapuis, J. Appl. Crystallogr., 2007, 40, 786; (d) P. W. Betteridge, J. R. Carruthers, R. I. Cooper, K. Prout and D. J. Watkin, J. Appl. Crystallogr., 2003, 36, 1487; (e) R. I. Cooper, A. L. Thompson and D. J. Watkin, J. Appl. Crystallogr., 2010, 43, 1100; (f) A. L. Thompson and D. J. Watkin, J. Appl. Crystallogr., 2011, 44, 1017; (g) G. M. Sheldrick, SHELX-2014 package, 2014.

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Footnote

† CCDC 954137, 1576950–1576952 and 1582718. For crystallographic data in CIF or other electronic format see DOI: 10.1039/c7dt04136e

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