Michele
Benedetti
*a,
Vincenza
Lamacchia
b,
Daniela
Antonucci
a,
Paride
Papadia
a,
Concetta
Pacifico
b,
Giovanni
Natile
b and
Francesco P.
Fanizzi
*a
aDipartimento di Scienze e Tecnologie Biologiche ed Ambientali, Università del Salento, Via Monteroni, I-73100 Lecce, Italy. E-mail: fp.fanizzi@unisalento.it; michele.benedetti@unisalento.it; Fax: +39 0832 298626; Tel: +39 0832 298867
bDipartimento di Chimica, Università degli Studi di Bari, Via E. Orabona 4, I-70125 Bari, Italy
First published on 3rd April 2014
The reactivity with acetylene of [PtX2(Me2phen)] (X = Cl, Br, I) complexes has been investigated. Whereas the chlorido species [PtCl2(Me2phen)] exhibits negligible reactivity at short reaction times, the bromido and iodido species [PtBr2(Me2phen)] and [PtI2(Me2phen)] lead initially to formation of Pt(II) five-coordinate complexes, [PtX2(η2-CHCH)(Me2phen)], that evolve to four-coordinate alkenyl complexes of the type [PtX(η1-E-CHCHX)(Me2phen)]. The alkenyl complexes, in the presence of excess acetylene, establish an equilibrium with the five-coordinate alkyne–alkenyl species [PtX(η1-E-CHCHX)(η2-CHCH)(Me2phen)] (X = Br, I). The π-bonded acetylene can be exchanged with free olefins or CO, affording the new alkene–alkenyl or carbonyl–alkenyl complexes [PtX(η1-E-CHCHX)(η2-olefin)(Me2phen)] and [PtX(η1-E-CHCHX)(CO)(Me2phen)]. The five-coordinate geometry of the alkyne–alkenyl and alkene–alkenyl complexes was assessed from NMR data and is fully consistent with that of a previously determined X-ray structure of [PtBr(η1-E-CHCHBr)(η2-CH2CH2)(Me2phen)].
In previous work we synthesized and characterized complexes with the Me2phen ligand, of the type [PtX2(Me2phen)] (X = halogen),21 showing considerable distortions from the regular square planar arrangement and an unusual chemical and electrochemical behavior, with respect to analogous complexes in which the phenanthroline has no substituents in the 2,9 positions.22 Because of steric interactions between ortho substituents of the phenanthroline and halogen ligands in cis positions, the square planar [PtX2(Me2phen)] complexes have a great tendency to add an external L ligand (L = CO, PPh3, DMSO, DMS, py, n-PrNH2, alkene, alkyne) to give the corresponding addition product.23,24 The reaction pathway is likely to contemplate the dissociation of one end of the N-donor chelate ligand, with formation of a tricoordinate intermediate, able to add an additional ligand (Scheme 1). Then, depending upon the electron withdrawing properties of the entered ligand, the Me2phen can remain monodentate, giving a tetra-coordinate complex21,24 or can coordinate the second end, to give a pentacoordinate, trigonal bipyramidal, species.25 Although it was not expected, intermediate cases are also possible.21,23,24
Therefore, when L is a very strong π acceptor ligand (such as an alkene or an alkyne; this class of ligands is indicated as L′ in Scheme 1), the electron density on the metal is strongly reduced by the π back-donation from the metal to the ligand. In this case both Me2phen nitrogen donors are coordinated to the metal core, in a five-coordinated trigonal bipyramidal structure, having the halogens in the apical positions and the Me2phen and L′ ligands in the equatorial plane. The observed Pt–N bonding distances are generally longer than the corresponding distances in [PtX2(Me2phen)] square planar species.
In contrast, in the case of ligands with weak or no π-acceptor capacity (such as py or n-PrNH2; this class of ligands is indicated as L′′ in Scheme 1), the second N-donor of the Me2phen remains uncoordinated and the [PtX2L′′(Me2phen)] complex is four-coordinate, square planar. However, also in the latter case the two halves of Me2phen are magnetically equivalent because of rapid exchange, in the NMR time scale, of the two nitrogens of Me2phen on the single platinum coordination site. Because of fast phenanthroline flipping, it was possible to distinguish between five-coordinate and four-coordinate [PtX2L(η1-Me2phen)] species only by X-ray diffraction studies in the solid state (where the flipping of the ligand is frozen) or by low-temperature NMR experiments. A somewhat intermediate case between five- and four-coordinate species was found when the L ligand had the π-acceptor capacity lower than ethylene.21,23,24
The distortion of the square planar complexes [PtX2(Me2phen)] depends chiefly on the steric interaction of the two ortho methyl substituents of Me2phen with the cis ligands, therefore the size of the halogen ligands plays a role. In the case of addition of an L′ ligand to give the pentacoordinate species [PtX2L′(Me2phen)], the iodide species is more reactive than the bromo species and this latter is more reactive than the chloro analogues. Both kinetic and thermodynamic data for formation of the [PtX2L′(Me2phen)] five coordinate species have been reported for the three halides and the barrier to rotation of the π ligand around the metal ligand bond was evaluated.25,26
Interestingly, in the case of acetylene addition to the square planar [PtBr2(Me2phen)] complex, the equilibrium constant for [PtBr2(η2-HCCH)(Me2phen)] formation could not be measured because of further reaction with the excess acetylene. In the present work we report further investigation, arising from that original observation, leading to the discovery of an interesting alkyne insertion reaction into a Pt–X bond, giving σ bonded alkenyl complexes.
Scheme 2 A possible mechanism for the formation of acetylene–alkenyl complexes. The coordinated alkyne can be easily substituted by other π-acceptor ligands (CH2CH2 and CO are shown). |
Complex | Me2phena | |||||
---|---|---|---|---|---|---|
Me(2,9) | CH(3,8) | CH(4,7) | CH(5,6) | η2-CHCH | η1-E-CHCHX | |
a The (3JH–H), [JH–Pt] and [nJPt–C] values are given, where assigned. c = cis, g = geminal. | ||||||
5 | 3.25 [7] | 7.57 d(8) | 8.33 d(8) | 7.75 | — | 7.55 d(14) [62] CHα,g |
2.81 | 7.55 d(8) | 8.25 d(8) | 5.08 d(14) [27] CHβ,c | |||
{28.50} | {126.85} | {136.31} | {125.50} | {118.39 Cα} | ||
{29.52} | {127.10} | {136.71} | {93.64 Cβ} | |||
6 | 3.46 | 7.79 d(8) | 8.31 d(8) | 7.84 | 3.73[68] CH | 5.89 d(13) [42] CHα,g |
4.63 d(13) [35] CHβ,c | ||||||
{28.94} | {125.95} | {137.86} | {125.86} | {32.87} | {119.01 [856] Cα} | |
{93.88 [62] Cβ} | ||||||
8 | 3.50 | 7.84 d(8) | 8.36 d(8) | 7.90 | 3.73 [68] CH | 6.26 d(14) [37] CHα,g |
4.55 d(14) [38] CHβ,c |
It was also observed that in the presence of a strong excess of acetylene the equilibrium could be shifted toward the symmetric compound (6). On the basis of previous observations, the first species (5), containing an asymmetric Me2phen, is consistent with a square planar complex, containing a chelated Me2phen, a bromide, and a σ-bonded β-bromo-alkenyl ligand ([PtBr(η1-E-CHCHBr)(Me2phen)] (5)). Besides the asymmetry of the chelated Me2phen, also consistent with this structure is the observation of 195Pt coupling (7 Hz) only for one Me (that cis to the σ-bonded alkenyl and trans to the bromido ligand) while the second Me (that trans to the σ bonded alkenyl) is expected to have a negligible coupling with 195Pt due to the lengthening of the Pt–N bond. The second species 6, containing a symmetric Me2phen, is consistent with a trigonal bipyramidal complex containing a Br− and a β-bromo-alkenyl in apical positions, and a Me2phen and an acetylene in the trigonal plane ([PtBr(η1-E-CHCHBr)(η2-CHCH)(Me2phen)] (6)). The different position of the alkenyl ligand in compound 5 (in the square-planar coordination plane) and in compound 6 (in the apical position of a pentacoordinate system in which the Me2phen is in the trigonal plane), results in a considerable deshielding of the alkenylic protons in complex 5 (7.55α,geminal and 5.08β,cis ppm) with respect to complex 6 (5.89α,geminal and 4.63β,cis ppm, Table 1). This effect is more pronounced for protons in the α position, geminal to the metal, with respect to protons in the β position. An analogous shift of alkenylic protons, to lower frequency, was observed on passing from the square planar Pt(II) complex trans-[PtCl(η1-Z-CHCHCl)(PPh2Me)2] to the octahedral Pt(IV) species trans-[PtCl3(η1-Z-CHCHCl)(PPh2Me)2].27
In both complexes 5 and 6, the 1H-NMR data (Table 1) also show a 14 Hz coupling constant between the two alkenyl protons. This is a clear indication that the two hydrogen atoms are in trans positions with respect to the double bond.28,29 Moreover, the coupling constants between β-proton and 195Pt (42 and 62 Hz for complexes 5 and 6, respectively) are smaller than corresponding coupling constants in complexes in which the β-proton and 195Pt are trans to one another (≈ 100–200 Hz30), thus confirming the relative cis position of Pt and β-proton.
As expected for five-coordinate complexes, the π-acetylene protons undergo a high frequency shift of about 1 ppm with respect to free alkyne and are coupled with 195Pt (2JPt–H in the range of 50–65 Hz). A similar effect, but to a smaller extent, is observed for protons on carbons in the α position to the triple bond.2613C-NMR data of complexes 5 and 6 are in agreement with the suggested structures (Table 1).
The four-coordinate alkenyl species [PtBr(η1-E-CHCHBr)(Me2phen)] (5), formed by alkyne insertion in the Pt–Br bond of [PtBr2(Me2phen)] (2), reacts further with acetylene to form the alkyne–alkenyl five-coordinate product [PtBr(η1-E-CHCHBr)(η2-CHCH)(Me2phen)] (6). The equilibrium between 5 and 6 can be shifted toward the five-coordinate complex by using a strong excess of free alkyne (Scheme 2, Fig. 1).
By exchanging the acetylene with ethylene in compound 6, the compound [PtBr(η1-E-CHCHBr)(η2-CH2CH2)(Me2phen)] (7) can be obtained. The NMR spectra (1H, 13C, [1H–1H]-NOESY and [1H–13C]-HSQC) show the pattern typical of a symmetrically coordinated Me2phen (Fig. 2–4, 3S†). A 1H singlet, resonating at 3.31 ppm, accounting for six protons, and giving a cross peak with a carbon at 28.76 ppm (3JPt–C = 124 Hz), can be attributed to the two Me2phen methyls. A 1H singlet at 7.87 ppm, accounting for two protons, giving a cross peak with a carbon at 126.22 ppm, can be assigned to Me2phen CH's in positions 5 and 6. Two 1H doublets, at 7.78 and 8.34 ppm, accounting for two protons each and giving cross peaks with two carbons at 126.22 and 137.87 ppm can be attributed to Me2phen CH's in positions 3 and 8 and in positions 4 and 7, respectively. Two second order multiplets at 3.32 and 2.64 ppm (belonging to an AA′XX′ system), are coupled with 195Pt (2JPt–H = 68 and 65 Hz, respectively) and give HSQC cross peaks with a carbon at 32.25 ppm (1JPt–C = 343 Hz). These signals are assigned to the η2-coordinated ethylene. Finally, two proton doublets at 5.98 (2JPt–H = 41 Hz) and 4.66 ppm (3JPt–H = 48 Hz) and giving cross peaks with two carbons at 119.01 (1JPt–C = 882 Hz) and 94.32 (2JPt–C = 78 Hz) ppm, respectively, are assigned to the α and β protons of the η1-coordinated alkenyl.
Fig. 3 Expansion of the 2D [1H,1H]-NOESY spectrum (CDCl3, alkene–vinylic region) of [PtBr(η1-E-CHCHBr)(η2-CH2CH2)(Me2phen)] (7). |
Fig. 4 Expansion of the 2D [1H,13C]-HSQC spectrum (vinylic region) of complex [PtBr(η1-E-CHCHBr)(η2-CH2CH2)(Me2phen)] (7). |
The Me2phen and alkenyl 1H NMR signals of complex 7 are only slightly shifted with respect to the corresponding signals in complex 6. Moreover, the 2,9 methyl signal of Me2phen (δ = 3.31 ppm) has [1H,1H]-NOESY cross-peaks with both alkenyl protons (δ = 5.98 and 4.66 ppm). A 2D [1H,1H]-NOESY spectrum (Fig. 3) allowed assigning the two sets of alkene protons for [PtBr(η1-E-CHCHBr)(η2-CH2CH2)(Me2phen)] (7). The non-equivalence of the alkene protons is generated by the two different apical ligands. Only the most shielded proton signal of the coordinated alkene (δ = 2.64 ppm) shows cross-peaks with the protons of the bromo-alkenyl moiety, (the more intense peak is with the CHα proton). Therefore, the signal at 2.64 ppm is assigned to the pair of olefin protons facing the alkenyl ligand, while the more deshielded signal at 3.32 ppm is assigned to the protons facing the bromido ligand.
Altogether the NMR data are consistent with a complex of the type [PtBr(η1-E-CHCHBr)(η2-CH2CH2)(Me2phen)] (7), with bromido and β-bromo-vinylic ligands in apical positions, and the Me2phen and the π-ethylene in the trigonal plane (Table 2 and Fig. 2–4, 3S†), similar to previously reported Pt(II) complexes with trigonal bipyramidal geometries.31–39
Complex | Me2phena | |||||
---|---|---|---|---|---|---|
Me(2,9) | H(3,8) | H(4,7) | H(5,6) | η2-CH2CHR | η1-E-CHCHX | |
a The (3JH–H), [JH–Pt] and [nJPt–C] values are given, where assigned. b syn and anti refer to the structures with the methyl substituent(s) of the π bonded alkene pointing to the alkenyl or bromine, bounded to platinum in axial positions, respectively. c The signals of phenanthroline protons were not assigned to the respective syn and anti isomers. | ||||||
7 | 3.31 | 7.78 d(8) | 8.34 d(8) | 7.87 | 3.32 dd (4) [68] 2CH | 5.98 d(13)[41] CHα,g |
2.64 dd (4) [65] 2CH | 4.66 d(13)[48] CHβ,c | |||||
{28.76 [124]} | {126.22} | {137.87} | {126.22} | {32.25 [343]} | {119.01 [882] Cα} | |
{94.32 [78] Cβ} | ||||||
12 | 3.30 | 7.78 d(8) | 8.33 d(8) | 7.87 | 3.49 dd (4) [82] 2CH | 6.28 d(13)[24] CHα,g |
2.63 dd (4) [66] 2CH | 4.53 d(13)[38] CHβ,c | |||||
{30.07 [106]} | {127.12} | {138.77} | {127.12} | {31.85 [342]} | {131.45 [850] Cα} | |
{65.00 [56] Cβ} | ||||||
syn-10b,c | 3.42 | 7.81 d(8) | 8.33 d(8) | 7.85 | 2.67 d (11) [34] CHc | 6.27 d(13)[35] CHα,g |
3.36 | 7.79 d(8) | 8.33 d(8) | 7.84 | 4.02 m [91] CHg | 4.73 d(13)[32] CHβ,c | |
3.33 | 7.75 d(8) | 8.30 d(8) | 3.53 d(8) [88] CHt | |||
3.30 | 8.29 d(8) | 1.26 d(6) [69] CH3 | ||||
anti-10b,c | 3.36 d(11) CHc | 5.97 d(13)[28] CHα,g | ||||
3.07 m[63] CHg | 4.67 d(13)[32] CHβ,c | |||||
2.74 d(8) [30] CHt | ||||||
1.65 d(6) [57] CH3 | ||||||
syn-11b,c | 3.42 | 7.77 d(8) | 8.29 d(8) | 7.83 | 4.14 qd(5,2) [96] CH | 6.36 d(13)[39] CHα,g |
3.36 | 7.76 d(8) | 8.29 d(8) | 7.82 | 1.19 dd(5,2) [61] CH3 | 4.62 d(13)[28] CHβ,c | |
anti-11b,c | 3.14 qd(5,2) [83] CH | 5.96 d(13)[26] CHα,g | ||||
1.59 dd(5,2)[53] CH3 | 4.68 d(13)[33] CHβ,c | |||||
13 | 3.38 | 7.74 d(8) | 8.32 d(8) | 7.83 | — | 6.41 d(14)[54] CHα,g |
5.77 d(14)[48] CHβ,c | ||||||
14 | 3.30 | 7.78 d(8) | 8.33 d(8) | 7.87 | — | 6.28 d(13)[24] CHα,g |
4.53 d(13)[36] CHβ,c |
The single crystal X ray structure of complex 7 was also preliminarily reported (see Fig. 6S and Tables 1S, 2S†).40
The reaction with acetylene, performed in the case of the iodo species [PtI2(Me2phen)] (3), shows the immediate formation of a five-coordinate species with the alkyne π-bonded to platinum, [PtI2(η2-CHCH)(Me2phen)]; which, subsequently, converts completely, in the presence of a large excess of tetra(n-Bu)ammonium iodide, Bu = butyl, into another species characterized by vinylic protons at 6.26 and 4.55 ppm. Most likely the latter species is the alkyne–alkenyl complex [PtI(η1-E-CHCHI)(η2-CHCH)(Me2phen)] (8), (Fig. 1S†). In this case the excess iodide, in solution, seems necessary to favor a faster formation of the reactive unobserved intermediate [PtI(η1-E-CHCHI)(Me2phen)]). In this case the formation of the alkyne–alkenyl complex is not quantitative even operating in the presence of excess acetylene. For long reaction times, it is possible to observe complete consumption of [PtI2(η2-CHCH)(Me2phen)] (2 days) and formation of a brown precipitate. The 1H-NMR spectrum of the CDCl3 soluble fraction showed several 1H-NMR signals in the vinylic region, as is generally observed in the case of formation of polymeric species. In contrast, if the reaction between [PtI2(Me2phen)] (3) and acetylene is performed in the presence of a large excess of N(n-Bu)4I (30:1), the pentacoordinate alkyne–alkenylic product [PtI(η1-E-CHCHI)(η2-CHCH)(Me2phen)] (8) is obtained in quantitative yield and the reaction is faster (complete consumption of the starting species 3 in ≈2.5 h). Unlike the bromo species 2, the iodo species [PtI2(Me2phen)] (3) reacts with acetylene without detectable formation of the intermediate square planar alkenylic species [PtI(η1-E-CHCHI)(Me2phen)] (9). This is probably due to the higher reactivity of complex 9, with respect to the analogous bromo derivative, for addition of an η2-alkyne and direct formation of the five-coordinate species, a consequence of the greater steric hindrance of iodine with respect to bromine.
Interestingly, the pentacoordinate akyne–alkenyl complexes can be transformed in the more stable alkene–alkenyl complexes [PtX(η1-E-CHCHX)(η2-alkene)(Me2phen)], X = Br (alkene = ethylene, 7; propene, syn and anti-10; cis-2-butene, syn and anti-11, Table 2) or I (alkene = ethylene, 12), and carbonyl–alkenyl complexes [PtX(η1-E-CHCHX)(CO)(Me2phen)], X = Br (13) or I (14), by simply saturating the solution of the alkyne–alkenyl complex with the alkene or CO, respectively (Scheme 2, Table 2).
In the case of propene and cis-2-butene, due to the hindered rotation of the η2-coordinated alkene, a 1:1 mixture of the two possible isomers was obtained. NMR data referring to the alkene–alkenyl complexes are reported in Table 2. The 1H NMR spectra of the alkene–alkenyl complexes of 1-propene (10) and of cis-2-butene (11) have been interpreted on the basis of bidimensional COSY and NOESY spectra (Fig. 4S and 5S†). For five-coordinated alkenyl complexes, on the basis of 1H NMR data (integrated signals), the equilibrium constant for the ethylene–acetylene exchange reaction (T = 25 °C; Keq ≈ 6.3), Scheme 2, was also calculated.
A possible mechanism for the formation reaction of the alkyne–alkenyl complexes is depicted in Scheme 2. First, a pentacoordinate [PtX(η1-E-CHCHX)(η2-CHCH)(Me2phen)] complex can be formed from the square planar [PtX2(Me2phen)] complex, via dissociation of one end of Me2phen and formation of a T-shaped intermediate, as previously demonstrated in similar complexes, followed by addition of the alkyne.16,17,41 The formed five-coordinate complex can then be in equilibrium with a square planar cationic species formed by spontaneous dissociation of a halide (X−).42 The X− nucleophile can therefore give an exo nucleophilic attack on the π-bonded alkyne, giving a square planar complex with a platinum σ-bonded β-halogeno-vinylic group having the metal and the halogen in trans positions with respect to the double bond. Further alkyne addition gives finally the alkyne–alkenyl complex. The known higher reactivity, as a nucleophile, of the bromide with respect to iodide in organic solvents, accounts for the slower reaction of the iodo species 3, with respect to the bromo species 2, for formation of the β-halogen-alkenyl derivative. The proposed mechanism for alkyne insertion into a Pt–X (X = Br, I) bond is different from that proposed for the insertion in the Pt–O bond of five-coordinated alkene derivatives.43 Interestingly, the nucleophilic attack of X− on the π-bonded alkyne extends to halides the possibility of acting as nucleophiles toward unsaturated molecules π bonded to cationic complexes of platinum(II).8–11,13,15,23,25,28,29,41,42
Footnote |
† Electronic supplementary information (ESI) available. See DOI: 10.1039/c4dt00679h |
This journal is © The Royal Society of Chemistry 2014 |