Article pubs.acs.org/Organometallics
Alkyne Hydroamination and Trimerization with Titanium Bis(phenolate)pyridine Complexes: Evidence for Low-Valent Titanium Intermediates and Synthesis of an Ethylene Adduct of Titanium(II) Ian A. Tonks, Josef C. Meier, and John E. Bercaw* Arnold and Mabel Beckman Laboratories of Chemical Synthesis, California Institute of Technology, Pasadena, California 91125, United States S Supporting Information *
ABSTRACT: A class of titanium precatalysts of the type (ONO)TiX2 (ONO = pyridine-2,6-bis(4,6-di-tert-butylphenolate); X = Bn, NMe2) has been synthesized and crystallographically characterized. The (ONO)TiX2 (X = Bn, NMe2, X2 = NPh) complexes are highly active precatalysts for the hydroamination of internal alkynes with primary arylamines and some alkylamines. A class of titanium imido/ligand adducts, (ONO)Ti(L)(NR) (L = HNMe2, py; R = Ph, tBu), have also been synthesized and characterized and provide structural analogues to intermediates on the purported catalytic cycle. Furthermore, these complexes exhibit unusual redox behavior. (ONO)TiBn2 (1) promotes the cyclotrimerization of electron-rich alkynes, likely via a catalytically active TiII species that is generated in situ from 1. Depending on reaction conditions, these TiII species are proposed to be generated through Ti benzylidene or imido intermediates. A formally TiII complex, (ONO)TiII(η2-C2H4)(HNMe2) (7), has been prepared and structurally characterized.
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INTRODUCTION The inter- and intramolecular hydroamination of alkenes and alkynes has been catalyzed by a range of complexes of transition metals, lanthanides, and even main-group elements.1 Among this broad range of catalysts, group 4 complexes2 have been found to be excellent catalysts for the intermolecular hydroamination of alkynes. Bergman and others have investigated the mechanism2 of the group 4 catalyzed reaction and have found that it typically proceeds first by protonolysis by an amine and subsequent formation of a transient metal imido species, followed by [2 + 2] addition with an alkyne to generate an azametallacyclobutene that can be protonolyzed by another 1 equiv of amine to complete the catalytic cycle (Scheme 1). A common catalyst deactivation pathway involves dimerization of a low-coordinate Ti−imido intermediate, typically discouraged by utilizing bulky amines or by operating at high temperatures to favor the monomer. While the product of this reaction, either an imine or enamine, might often be more easily formed via amine condensation with a ketone, alkyne hydroamination remains a useful synthetic toolparticularly because of its atom economy. Recently our group3 and others4 have been investigating pyridine-linked bis(phenoxide), LX2 type pincer ligands for early-transition-metal catalysts for olefin polymerization. Earlytransition-metal complexes of these ONO ligands are very thermally robust due to their rigid, all-aryl backbone. In light of reports that phenoxide-based 5 titanium complexes are © XXXX American Chemical Society
precatalysts for intermolecular alkyne hydroamination, we envisioned that ONO titanium complexes might also be competent and long-lived catalysts. Investigations of the scope and mechanism of catalysis revealed that, in addition to alkyne hydroamination, in the absence of amines these same precatalysts promote the cyclotrimerization of alkynes, likely via reductive elimination of arene to afford a transient (ONO)TiII species. The synthesis and structural characterization of the ethylene adduct (ONO)TiII(η2-C2H4)(NHMe2) provides support for this hypothesis.
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RESULTS AND DISCUSSION Synthesis and Characterization of Precatalysts. (ONO)TiBn2 (1; ONO = pyridine-2,6-bis(4,6-di-tert-butylphenolate)) was synthesized via protonolysis of TiBn4 with (ONO)H2 following a literature procedure3c (Scheme 2). Salt metathesis of TiCl2(NMe2)2 and the dipotassium salt of the ligand (ONO)K2 generates the bis(amide) (ONO)Ti(NMe2)2 (2). Similarly, salt metathesis of TiCl2(HNMe2)2(NPh) with (ONO)K2 yields the phenylimido complex (ONO)Ti(HNMe2)(NPh) (3). A series of (ONO)Ti imido complexes can be synthesized by utilizing differently substituted Ti−imido starting materials of the type TiCl2(L)2(NR) (L = HNMe2, py, R = alkyl, aryl; for 4, R = tBu, L = py). Finally, the pyridineReceived: January 29, 2013
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dx.doi.org/10.1021/om400080g | Organometallics XXXX, XXX, XXX−XXX
Organometallics
Article
Scheme 1
Scheme 2
form adducts, whereas the larger congener (ONO)ZrBn2 easily coordinates a sixth ligand. On the other hand, the comparatively electron-poor dichloride, unlike 1 and 2, readily binds a pyridine to form a six-coordinate, Cs-symmetric complex in the solid state (Figure 1). 3 is not readily crystallized, but the related complex (ONO)Ti(py)(NtBu) (4) can be crystallized from a 5/1 pentane/toluene solution at −30 °C. The Cs-symmetric ONO ligand in 4 occupies two equatorial sites as in 2, and the linear imido functionality occupies the third equatorial site of the distorted trigonal bipyramid. In a [2 + 2] hydroamination mechanism, Ti−imido species are key intermediates along the catalytic cycle. Thus, 4 could provide a structural analogue to a catalytically relevant [(ONO)TiNR] intermediate. In this case, an incoming alkyne would likely occupy the same coordination site as pyridine in 4. Catalytic Hydroamination of Alkynes. Table 1 summarizes the hydroamination of alkynes with primary amines as catalyzed by 1. Mixing 1 with amine and alkyne at room temperature results in no reaction; however, 1H NMR reveals
stabilized dichloride complex (ONO)TiCl2(py) (6) was synthesized through aminolysis of TiCl2(NMe2)2 with (ONO)H2, followed by treatment with excess pyridine. In the absence of pyridine, the HNMe2 adduct (ONO)TiCl2(HNMe2) (5) is obtained, although this complex loses some HNMe2 to form a mixture of (ONO)TiCl2 and (ONO)TiCl2(HNMe2) upon workup. We were unable to synthesize (ONO)TiCl2-type complexes through salt metathesis of TiCl4 or TiCl4(THF)2 with (ONO)K2, presumably because the deprotonated ligand reduces the titanium starting material. The crystal structure of the C2-symmetric 1 has been previously reported.3c Interestingly, in the solid state 2 has a Cssymmetric ONO ligand with the two phenolate arms occupying equatorial sites of a distorted trigonal bipyramid (Figure 1). A Cs-symmetric structure is likely the electronically preferred3d geometry for π-loaded five-coordinate ONO complexes, whereas five-coordinate ONO complexes without additional π donors prefer C2 arrangements. Due to the small, electron-rich Ti metal center, neither 1 nor 2 can easily accommodate a sixth ligand: THF, Et2O, pyridine, and PMe3 do not coordinate to B
dx.doi.org/10.1021/om400080g | Organometallics XXXX, XXX, XXX−XXX
Organometallics
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Figure 1. Thermal ellipsoid drawings (50% probability level) of 2 (top), 4 (middle), and 6 (bottom). Selected bond lengths (Å) and angles (deg) are as follows. Complex 2: Ti1−N1, 2.3982(3); Ti1−N2, 1.9049(2); Ti1−N3, 1.8707(2); Ti1−O1, 1.8734(2); Ti1−O2, 1.8756(2). Complex 4: Ti1− N1, 2.2192(1); Ti1−N2, 1.6877(1); Ti1−N3, 2.2116(1); Ti1−O1, 1.9236(1); Ti1−O2, 1.9320(1); Ti1−N2−C34, 170.97. Complex 6: Ti1−N1, 2.2941(1); Ti1−N2, 2.2542(1); Ti1−O1, 1.8132(1); Ti1−O2, 1.8487(1). Solvent molecules and H atoms are removed for clarity.
that upon heating at 90 °C the precatalyst is rapidly consumed, producing 2 equiv of toluene that result from protonolysis of the benzyl ligands by amine. For reactions with 2-butyne or 1phenyl-1-propyne, 20 turnovers (based on amine) are achieved in less than 1 h, while reactions with the electron-poor diphenylacetylene are substantially slower. Mixtures of the E and Z imine isomers are obtained. In the case of the hydroamination of the unsymmetrically substituted 1-phenyl1-propyne, 1-phenylpropan-2-ylidene imines were obtained exclusively. Electron-rich, sterically unencumbered arylamines are particularly good substrates, and even some relatively bulky arylamines (such as o-toluidine) undergo reaction. Substrates with excessive steric bulk in the ortho position or with strongly electron withdrawing groups are unreactive. Bulky alkylamines such as iPrNH2 react, albeit extremely slowly, in comparison to the arylamines. Entry 11 indicates that 1 is significantly more effective for the hydroamination of 1-phenyl-1-propyne than the similar Beller bulky bis(aryloxide)Ti-catalyzed5 hydroamination system (48 h, 130 °C, 10 turnovers, in comparison to 1 h, 90 °C, >20 turnovers for 1).
Sterically demanding amines such as 2,6-dimethylaniline are usually among the better substrates6 for many Ti-based catalysts (such as that derived from Cp2TiMe2), because the increased steric bulk prevents catalyst deactivation through imido dimerization (Scheme 1). For 1, however, sterically demanding arylamines (such as 2,6-dimethylaniline) are unreactive. Apparently the bulky, tridentate ONO ancillary ligand prevents coordination of bulky amines. While the steric bulk of the ONO ligand hampers reactivity with bulky amines, it also inhibits imido dimerization in smaller arylamines so that 1 exhibits high activities for these substrates.7 Reactions of substrates with no ortho or meta aryl substitution (entries 1−3 and 5, for example) precipitate an unknown Ti species (possibly the imido dimer) from solution near the end of the reaction as the substrate concentrations decrease. These reactions likely do not proceed through a heterogeneous process upon precipitation, as the filtrate obtained after filtering the reaction mixture is still catalytically competent. For reactions with bulkier amines (entries 2 and 7) the reaction solutions remain homogeneous. C
dx.doi.org/10.1021/om400080g | Organometallics XXXX, XXX, XXX−XXX
Organometallics
Article
Table 1. Catalytic Hydroamination of Alkynes with (ONO)TiBn2 (1)a
entry
R1
R2
R3
time (h)
yield, % (E:Z)
1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17b 18b 19b 20b 21b
Me
Me
Me
Ph
Ph o-CH3C6H4 p-CH3C6H4 2,6-Me2C6H3 p-MeOC6H4 p-CF3C6H4 3,5-tBu2C6H3 2,4-tBu2C6H3 Bn i Pr Ph o-CH3C6H4 p-CH3C6H4 p-MeOC6H4 3,5-tBu2C6H3 Bn Ph o-CH3C6H4 p-CH3C6H4 p-MeOC6H4 3,5-tBu2C6H3
1 1 1 1 1 1 1 1 1 140 1 1 1 1 1 1 8 8 8 8 1
100 (5:1) 100 (5.6:1) 100 (5:1) 0 100 (5.2:1) 0 100 (4.9:1) 0 0 95 (5:1) 100 (3:1) 100 (3.6:1) 100 (3:1) 100 (3.6:1) 100 (2.3:1) 0 66 (1:0) 83 (1:0) 77 (1:0) 76 (1:0) 100 (1:0)
Ph
Ph
Figure 2. Reaction time course of diphenylacetylene hydroamination with 3,5-di-tert-butylaniline catalyzed by 1−3 at 75 °C.
should be the same for all three. While 1 and 2 do proceed at roughly the same rate, 3 catalyzes the reaction at roughly half the rate of 1. Because the reaction using 2 proceeds at the same rate as that using 1 and also produces HNMe2 over the course of the reaction, we do not believe that HNMe2 inhibition is the cause for lower reaction rates with 3. Rather, we suspect that inefficient catalyst activation lowers the overall rate: in order to enter the catalytic cycle, 3 must lose HNMe2 to form a sterically unencumbered, four-coordinate phenylimido species that, as evidenced in earlier reactions, could easily dimerize and deactivate. Supporting this hypothesis, 3 generates a substoichiometric amount of the expected product of activation, N(1,2-diphenylethylidene)aniline, indicating that some of the precatalyst never undergoes a [2 + 2] reaction with alkyne. Although its activity is lower, the competency of 3 for hydroamination and the observation of the aniline-hydroaminated product N-(1,2-diphenylethylidene)aniline give further evidence that these [(ONO)Ti]-catalyzed reactions proceed through a typical imido + alkyne [2 + 2] addition mechanism. (ONO)TiII-Catalyzed Alkyne Cyclotrimerization. When (ONO)TiBn2 (1) was allowed to react under catalytic conditions for 14 h with 10 equiv of 3,5-di-tert-butylaniline and 30 equiv of dimethylacetylene, GC-MS revealed parent ion peaks for hexamethylbenzene and N-(3,5-di-tert-butylphenyl)2,3,4,5-tetramethylpyrrole in addition to that for the hydroaminated product (Scheme 3 and Figure 3). Both of these side products were generated in low yield (
