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OVER 45 (Mayores de 45 años: las causas de la exclusión laboral
As attempts at generating a platinum-alkyl pincer complex [(PCP)PtR] from the Pt(0) norbornene dimer 14 were unsuccessful, the Pt(II) compound [PtMe2(hex)] (where hex = 1,5-hexadiene) was investigated for its utility as a precursor toward the synthesis of a platinum-methyl pincer complex [(PCP)PtMe]. It has been demon- strated in the literature that [(PCP)PtMe] complexes can be obtained in moderate yields directly from platinum dimethyl precursors.58
As for the corresponding platinum(0) reactions, the coordination chemistry of 1 to [PtMe2(hex)] was initially performed on a small scale in NMR tubes, allowing real-time monitoring of reaction progress by NMR spectroscopy. Reactions in both toluene-d8 and dichloromethane-d2 showed the formation of two major species 15
and 16 at room temperature. Each compound displayed 1H NMR signals consis-
tent with symmetrical, unmetallated aryl ligand backbones, and relatively small platinum-phosphorus couplings (≈ 2200 Hz) in the 31P NMR spectrum, indica-
tive of phosphorus coordination trans to a methyl group (which possess a large
trans influence). This allowed for the formulation of both 15 and 16 as cis- [(POCOPH)PtMe2]x species. Compounds 15 and 16 displayed markedly different
solubilities, and as such they were able to be separated and isolated by precipitation of the less soluble 16 by the addition of hexane to reaction mixtures in toluene. Analysis by HRMS indicated that the more soluble species 15 was the dimeric com- pound cis-[(POCOPH)PtMe2]2, with the [M+Na]+ion detected at m/z = 2147 amu.
No adequate mass spectrometry results were obtained for 16; in some cases traces of 15 were observed and in others no peaks attributable to a [(POCOPH)PtMe2]x
species were observed. Liquid Chromatography Mass Spectrometry (LCMS) was performed in order to overcome contamination of each species by minor amounts of the other; however, LCMS was unsuccessful in this respect, as both compounds either degraded or were retained on the column. As such, while the HRMS
data were consistent with the formulation of 15 as the dimeric compound cis- [(POCOPH)PtMe2]2, it was not able to be definitively established.
Compound 16 is likely to be a cyclic [(POCOPH)PtMe2]xoligomer of relatively low
molecular weight (x = 3 or 4); it is significantly less soluble than the dimeric 15 in common organic solvents, yet soluble enough that sufficient NMR data could be acquired for characterisation. It is highly unlikely to be a cis-monomer. Such species are well established for complexes of PCPH ligands with alkyl backbones (as the backbone can readily contort out of the coordination plane of the metal to minimise steric strain),95–97 but are seldom formed at room temperature in complexes with
aromatic ligand backbones, due to the demands of forming a rigid, eight-membered chelate ring.91 O O PR2 PR2 [PtMe2(hex)] solvent, rt where R = C6F5 and x > 2 O R2 P O P R2 Pt O O P R2 R2 P Pt Me Me Me Me CH2Cl2, 24 h, 63% toluene, 72 h, 78% + Pt R2 P R2 P O O x Me Me 15 16 1
Scheme 3.4 Formation of [(POCOPH)PtMe2]x species (15 and 16) from the re-
action of 1 with [PtMe2(hex)].
In the synthesis of 15 (Scheme 3.4), it was observed that longer reaction times and the use of toluene instead of dichloromethane increased the yield of the dimeric complex. This parallels observations in the synthesis of the analogous platinum(0) dimer 14. While the corresponding platinum(0) oligomer was not soluble enough to characterise, it was noted that the dimer synthesis proceeded more rapidly and with the formation of less insoluble white material in benzene and toluene than in dichloromethane. As mentioned above, this may be due to stabilising interactions from the aromatic solvent increasing the rate of reaction.
The platinum [(POCOPH)PtMe2]x compounds 15 and 16 possessed very similar
NMR spectroscopic data. However, in 1H NMR spectra of the two species, there
backbone. For the oligomer 16 this proton was observed between the other two aro- matic proton environments of the backbone at δH= 6.94 ppm, whereas for the dimer
15 this proton was the most upfield of all the aromatic proton signals, appearing at δH= 6.42 ppm. This observation of an upfield shift in H-2 again displayed parallels
to the norbornene dimer 14, where the H-2 signal was observed at δH = 6.35 ppm.
As the solid state structure of 14 displayed a distinct π-π interaction between the two ligand backbones, centred about H-2 (Figure 3.2), it is likely that this proton environment is shielded by the shared π-electrons, accounting for the observation of a upfield shift of H-2 in the two dimeric structures (Figure 3.3). Similar shielding of aromatic protons by π-stacking has been established in 1H NMR spectroscopy
of organic molecules.98 It would be very difficult for the oligomeric structure 16 to
adopt a conformation in solution possessing these intramolecular π-π interactions, and consequently 16 displayed an H-2 resonance at a similar chemical shift to the other aromatic protons of the backbone.
Figure 3.3 Effect of π-π stacking on the 1H NMR spectra of compounds 14, 15,
and 16 in acetone-d6.
Reaction mixtures containing the [(POCOPH)PtMe2]x species 15 and 16 were then
heated to promote metallation and formation of the pincer [(POCOP)PtMe] species. Thermolysis of toluene solutions at 90 ◦C was seen to produce predominantly one
new species, 17. NMR signals of the species were extremely broad, rendering 1H
NMR data of little use in structural assignment. However, the 31P NMR spectrum
displayed two broad singlets in a 1:1 ratio at 113.1 and 96.3 ppm, with platinum- phosphorus coupling constants of 2032 and 2722 Hz respectively. This indicated the presence of phosphorus donors both cis and trans to a methyl group; the high solubility of the species in toluene and the propensity of ligand 1 to form bridged
κ2-PP dimers (see below) suggested that the complex was likely to be dimeric. This
allowed for the tentative assignment of 17 as cis,trans-[(POCOPH)PtMe2]2. Similar cis,trans-dimers were isolated from the reaction of ligand 1 with platinum dichloride
and platinum chloromethyl precursors, and are subsequently discussed in detail. Metallation of 17 was not observed to any appreciable extent after 20 hours at 90 ◦C. Upon increasing the temperature to 100 ◦C, the formation of the desired
pincer species [(POCOP)PtMe] was detected (δP = 108.5 ppm, 1JPt-P = 3760 Hz;
verified by comparison with an independently synthesised sample, as is described in the Chapter 4). However, the appearance of this species was also accompanied by the formation of other unknown metallated pincer species, as well as the formation of perfluorinated biphenyl (C12F10), indicating the degradation of the ligand at these
elevated temperatures.
In an attempt to reduce the temperatures required for this metallation, identical reactions were carried out in acetone. It was hoped that a more polar solvent would assist with the proton transfer during metallation and stabilise any charged transi- tion states, minimising the energetic barrier to pincer complex formation. Reactions performed in acetone-d6 in sealed NMR tubes heated to 75 ◦C were observed again
to produce the broad resonances of 17, without the observation of any products resulting from metallation. The addition of the amine bases DMAP and DBU to toluene solutions of [(POCOPH)PtMe2]x was also attempted; however, as in the
analogous reactions with the platinum-norbornene dimer 14, only decomposition and a loss of signal in 31P NMR spectra was observed.
To investigate whether the difficulty in synthesising the metallated platinum methyl complex [(POCOP)PtMe] was due to the highly electron-deficient nature of the metal centre, or due to the inherent instability of 1 possessing highly polarised P−O bonds, reactions with the more electron-donating tert-butyl-substituted lig- and 3 were performed. The reaction between 3 and [PtMe2(hex)] was carried out in
benzene-d6 on an NMR scale. On standing at room temperature a number of prod-
ucts were initially observed by NMR spectroscopy. The major (and only identified) species in solution possessed two broad phosphorus signals in a 1:1 ratio at 88.7 and 48.3 ppm, with platinum-phosphorus coupling constants of 2268 and 1825 Hz respectively. The small downfield shift of the31P NMR signal of each of the phospho-
rus donors from those of the free ligand (where δP = 82.9 and 34.3 ppm), combined
with relatively small one bond platinum-phosphorus couplings (around 2000 Hz) was consistent with the formation of a κ2-PP bridged species cis-[(POCCPH)PtMe
2]x.
Pt R'2P PR2 Me Me Pt R'2P PR2 Me Me Pt R2P PR2 Me Me Pt R'2P PR'2 Me Me x x
Figure 3.4 The two possible structural isomers that [(POCCPH)PtMe2]x may
adopt in solution.
degree of deshielding than the bis(pentafluorophenyl)phosphinite on coordination to the platinum (with the δP moving downfield by 14.0 for the phosphine and
5.8 ppm for the phosphinite), as the more electron-donating CH2PtBu2 group con-
tributed more electron density to the platinum than the more electron-withdrawing OP(C6F5)2 group did. Due to this difference in σ-basicity, it may be expected that
initial coordination of the tert-butyl phosphine would be favoured over coordination of the pentafluorophenyl phosphinite, yielding a complex containing two distinct platinum centres (Figure 3.4, right). However, due to the broad nature of the phos- phorus resonances (full width at half height maximum of 75 and 98 Hz respectively) it is difficult to determine the exact coordination environment of the metal; the cis phosphorus-phosphorus coupling expected where different P-donors are coordinated to the same metal centre is on the order of tens of Hertz in similar platinum dimethyl complexes,99 meaning that such a coupling may be present but not resolved in this
instance.
On standing at room temperature, the NMR resonances of the [(POCCPH)PtMe2]x
species were observed to broaden even further, producing a large number of uniden- tified signals in the 31P NMR spectrum between 90 and 60 ppm. Thermolysis of the
reaction mixture at 60 ◦C for 48 hours produced only small amounts of the desired
[(POCCP)PtMe] pincer species (assigned on the agreement of 31P NMR data with
independently synthesised [(POCCP)PtMe], described in the Chapter 4). However, upon increasing the temperature to 85◦C for 24 hours, degradation of the platinum
methyl complex along with formation of perfluorinated biphenyl was observed. As such, the thermolysis of platinum dimethyl dimers did not proceed with sufficient selectivity to provide a viable route to metallated pincer complexes.