Cofactor Controlled Encapsulation of a Rhodium Hydroformylation
Catalyst
Lukas J. Jongkind, Johannes A. A. W. Elemans, and Joost N. H. Reek*
anie_201812610_sm_miscellaneous_information.pdf
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Supporting Information
©Wiley-VCH 2016
69451 Weinheim, Germany
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Experimental procedures
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General procedures
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Titration experiments
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HPFT-IR and catalysis
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CSI-MS
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Computational details
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NMR spectra
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Titration fitting and UV-VIS data
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Mass spectrometry data
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HP-IR spectra
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Catalyst characterization (
1H,
31P, NOESY NMR spectra)
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2D
1H-DOSY NMR spectra
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IR initial rate data
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Catalyst stability
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Selectivity determination
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Additional catalytic experiments
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XYZ coordinate file of the xTB calculations
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Experimental Procedures
General procedures. All reactions were performed under an inert atmosphere (N2 or Ar) using standard Schlenk techniques unless stated otherwise. CH2Cl2 was distilled over CaH2 under N2 atmosphere, acetonitrile was purified over a column using an SPS setup.
1-Octene was filtered over basic alumina prior to use, other reagents were used as received. Rh(acac)(CO)2 was used as received.
Tris-3-pyridyl phosphine 1,[1] 4,4’-dimethylviologen dihexafluorophosphate[2] and zinc porphyrin clip 2[2] were synthesized using
literature procedures.
Titration experiments. A stock solution of 2 (or 2 with 3 equivalents of the cofactor 4,4’-dimethylviologen dihexafluorophosphate) in a degassed mixture of freshly distilled CH2Cl2 and CH3CN (4:1, v/v) toluene, and a stock solution of guest 1 in the same solvent
mixture, containing the same concentration of 2 (or 2 with cofactor), were prepared respectively. Aliquots of 1 from the guest stock solution were added directly to a quartz cuvette containing the solution of 2 (or 2 with cofactor). Each titration was performed by around 70 measurements at 298 K. Up to ca. 80 guest equivalents (for addition to 2) or 25 equivalents (for addition to 2 with cofactor) were added. The progress of the titration was monitored by the shifts in the Q-bands (in the case of 2) or the Soret band (in the case of 2 + cofactor) of the porphyrin.
HP-FTIR and catalysis. High-pressure IR spectra were recorded using a specially modified autoclave.[3] The autoclave was flushed
with Ar for 20 minutes prior to use. The samples were then injected under Ar flow, after which the autoclave was flushed with syngas (CO/H2=1:1, 10 bar, 3x) and pressurized to the required pressure. Addition of Rh or substrate proceeded through a separate
container in the autoclave under slight overpressure of syngas (25 bar). A background was measured of the phosphine ligand, the zinc porphyrin clip and the cofactor (when added), after which Rh(acac)(CO)2 was added and formation of the active species was
monitored overnight. Then, 1-octene and decane (I.S.) were added to the autoclave and the formation of the product was followed for 24h. After this time the pressure was released and a GC sample was taken to determine the final conversion, yield and selectivity. GC separation of the hydroformylation products was performed on an Interscience Trace GC Ultra machine with a RTX-1 column (30 meter column, 0.25 mm internal diameter, 0.25 μm film thickness), initial temperature: 50 °C, hold for 2 minutes, ramp 10 °C/min to 300 °C, hold for 3 minutes. The linear product (nonanal) and 1-octene were calibrated against the internal standard (n-decane). It was assumed that the branched product would have the same response factor in the gas chromatograph. The conversion as monitored with IR was calibrated by taking a catalytic sample of a known absorption and determining the corresponding conversion and yield using the aforementioned GC method using n-decane as an internal standard. The ratio of linear to branched product as found by GC was confirmed by NMR, see S20 and S21.
CSI-MS. Mass spectra (CSI) were collected on an AccuTOF LC, JMS-T100LP Mass spectrometer (JEOL, Japan). Measurement conditions are as follows: Positive-ion mode; Needle voltage 2000V, Orifice 1 voltage 90V, Orifice 2 voltage 9V, Ring Lens voltage 22V, Orifice 30 °C, Desolvating Chamber 30 °C. The drying gas (N2) was held at –35 °C and the spray gas was held at –40 °C.
NMR spectra. NMR spectra were recorded on a NMR spectra were recorded on a Bruker AMX 300 (300.1 MHz, 75.5 MHz and 121.5 MHz for 1H, and 31P respectively) and reference to the solvent residual signal.
Computational details. The structure of the encapsulated catalyst in figure 3 was generated by compiling crystal structure data to one structure. The geometry optimizations of the complex was carried out using a tight-binding quantum chemical method (GFN-xTB) that mimics DFT and is useful for large molecular systems.[4]
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Titration fitting an UV-VIS data
Figure S1a. Fitted UV-vis titration curves (left: 562 nm; right: 597 nm) of 2 with 1 in CH2Cl2/CH3CN 4:1 (v/v). The dots represent the experimental data points, the
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[2] (M) [1] (M) A(562 nm) A(597 nm) 4,477E-5 0 0,72339 0,19308 4,477E-5 4,53234E-5 0,7212 0,19322 4,477E-5 9,0198E-5 0,72297 0,19529 4,477E-5 1,34631E-4 0,7237 0,19824 4,477E-5 1,78627E-4 0,72264 0,19769 4,477E-5 2,22195E-4 0,72231 0,19896 4,477E-5 2,6534E-4 0,72892 0,20237 4,477E-5 3,08068E-4 0,73091 0,2027 4,477E-5 3,50385E-4 0,73268 0,20701 4,477E-5 3,92297E-4 0,73333 0,20613 4,477E-5 4,3381E-4 0,73356 0,2085 4,477E-5 4,74929E-4 0,73729 0,20752 4,477E-5 5,1566E-4 0,7393 0,21078 4,477E-5 5,56009E-4 0,73958 0,21072 4,477E-5 5,95981E-4 0,7424 0,21301 4,477E-5 6,35581E-4 0,74301 0,21385 4,477E-5 6,74815E-4 0,74367 0,21625 4,477E-5 7,13687E-4 0,74454 0,21859 4,477E-5 7,52202E-4 0,74951 0,21703 4,477E-5 7,90365E-4 0,74403 0,21809 4,477E-5 8,28182E-4 0,74375 0,21745 4,477E-5 8,65656E-4 0,74919 0,21941 4,477E-5 9,02793E-4 0,74883 0,22201 4,477E-5 9,39596E-4 0,75818 0,22617 4,477E-5 9,76071E-4 0,75002 0,22223 4,477E-5 0,00101 0,75261 0,22297 4,477E-5 0,00105 0,75389 0,22365 4,477E-5 0,00108 0,75437 0,22566 4,477E-5 0,00112 0,75691 0,22708 4,477E-5 0,00115 0,75626 0,22776 4,477E-5 0,00119 0,76027 0,23215 4,477E-5 0,00126 0,75986 0,23275 4,477E-5 0,00132 0,76045 0,23342 4,477E-5 0,00139 0,76299 0,23459 4,477E-5 0,00145 0,76542 0,24016 4,477E-5 0,00152 0,76325 0,23907 4,477E-5 0,00158 0,76561 0,24383 4,477E-5 0,00164 0,76549 0,24074 4,477E-5 0,0017 0,76434 0,2408 4,477E-5 0,00176 0,76775 0,2419 4,477E-5 0,00182 0,77272 0,24482 4,477E-5 0,00188 0,77151 0,24934 4,477E-5 0,00194 0,77069 0,24898 4,477E-5 0,00199 0,77465 0,24877 4,477E-5 0,00205 0,7721 0,24933 4,477E-5 0,0021 0,77658 0,25383 4,477E-5 0,00216 0,77872 0,25097 4,477E-5 0,00221 0,78061 0,25645 4,477E-5 0,00226 0,77871 0,25382 4,477E-5 0,00231 0,78193 0,25736 4,477E-5 0,00236 0,78065 0,2577 4,477E-5 0,00246 0,78527 0,25887 4,477E-5 0,00256 0,7879 0,26197 4,477E-5 0,00265 0,78871 0,26187 4,477E-5 0,00274 0,79236 0,26689 4,477E-5 0,00283 0,79426 0,26882 4,477E-5 0,00291 0,79341 0,26783 4,477E-5 0,003 0,80081 0,27014 4,477E-5 0,00308 0,80164 0,27337 4,477E-5 0,00316 0,80051 0,27364 4,477E-5 0,00323 0,80858 0,27495 4,477E-5 0,00331 0,80683 0,28082 4,477E-5 0,00338 0,80791 0,2772 4,477E-5 0,00345 0,81021 0,27632 4,477E-5 0,00352 0,81407 0,27823 4,477E-5 0,00359 0,81824 0,283076
Figure S2a. Fitted UV-vis titration curves (left: 429 nm; right: 430 nm) of the 2-viologen complex with 1 in CH2Cl2/CH3CN 4:1 (v/v). The dots represent the
experimental data points, the solid lines the calculated fits assuming a 1:3 host-guest binding model. Conditions: [2] = 4.41 μM; [viologen] = 13.5 μM; [1]/[2-viologen] range 0 - 22.
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[2] (M) [1] (M) A(429 nm) A(430 nm) 4,41E-6 0 1,2028 1,09674 4,41E-6 1,14129E-6 1,20282 1,10329 4,41E-6 2,27129E-6 1,20525 1,10998 4,41E-6 3,39015E-6 1,20601 1,11421 4,41E-6 4,49804E-6 1,20489 1,11811 4,41E-6 5,59512E-6 1,20458 1,1222 4,41E-6 6,68155E-6 1,21257 1,12591 4,41E-6 7,75749E-6 1,22021 1,1227 4,41E-6 8,82308E-6 1,21053 1,1303 4,41E-6 9,87847E-6 1,21869 1,14182 4,41E-6 1,09238E-5 1,21791 1,14739 4,41E-6 1,19592E-5 1,22451 1,1391 4,41E-6 1,29849E-5 1,22347 1,14511 4,41E-6 1,40009E-5 1,22499 1,15589 4,41E-6 1,50075E-5 1,22977 1,16437 4,41E-6 1,60047E-5 1,22851 1,16199 4,41E-6 1,69926E-5 1,236 1,16571 4,41E-6 1,79714E-5 1,2362 1,16997 4,41E-6 1,89413E-5 1,24419 1,17876 4,41E-6 1,99023E-5 1,24546 1,1785 4,41E-6 2,08545E-5 1,24651 1,18914 4,41E-6 2,17982E-5 1,24937 1,18982 4,41E-6 2,27333E-5 1,24872 1,19286 4,41E-6 2,36601E-5 1,25704 1,19995 4,41E-6 2,45786E-5 1,25821 1,2029 4,41E-6 2,54889E-5 1,26385 1,20804 4,41E-6 2,63912E-5 1,25748 1,20914 4,41E-6 2,72855E-5 1,26518 1,21809 4,41E-6 2,81719E-5 1,27143 1,21896 4,41E-6 2,90507E-5 1,27168 1,2218 4,41E-6 2,99217E-5 1,27328 1,22922 4,41E-6 3,16414E-5 1,28187 1,22889 4,41E-6 3,33316E-5 1,2874 1,2415 4,41E-6 3,49932E-5 1,29035 1,24553 4,41E-6 3,66269E-5 1,28959 1,24622 4,41E-6 3,82333E-5 1,29755 1,25675 4,41E-6 3,98132E-5 1,30536 1,25486 4,41E-6 4,13672E-5 1,31007 1,26563 4,41E-6 4,28959E-5 1,30937 1,27008 4,41E-6 4,44E-5 1,31288 1,26838 4,41E-6 4,588E-5 1,31277 1,28002 4,41E-6 4,73365E-5 1,32493 1,28185 4,41E-6 4,87701E-5 1,32005 1,28657 4,41E-6 5,01813E-5 1,32443 1,28902 4,41E-6 5,15705E-5 1,32662 1,29464 4,41E-6 5,29385E-5 1,32954 1,30186 4,41E-6 5,42855E-5 1,33177 1,30111 4,41E-6 5,56121E-5 1,33428 1,30224 4,41E-6 5,69188E-5 1,33546 1,311 4,41E-6 5,8206E-5 1,33996 1,31273 4,41E-6 5,94741E-5 1,34312 1,31685 4,41E-6 6,19547E-5 1,3508 1,31948 4,41E-6 6,4364E-5 1,35269 1,32665 4,41E-6 6,6705E-5 1,35594 1,33038 4,41E-6 6,89804E-5 1,3575 1,33546 4,41E-6 7,11931E-5 1,36545 1,33049 4,41E-6 7,33456E-5 1,37269 1,34967 4,41E-6 7,54403E-5 1,37415 1,3534 4,41E-6 7,74795E-5 1,37882 1,35375 4,41E-6 7,94654E-5 1,37397 1,35499 4,41E-6 8,14E-5 1,38023 1,35889 4,41E-6 8,32854E-5 1,38221 1,36487 4,41E-6 8,51233E-5 1,38803 1,36572 4,41E-6 8,69155E-5 1,3881 1,37628 4,41E-6 8,86638E-5 1,392 1,37302 4,41E-6 9,03697E-5 1,3909 1,375 4,41E-6 9,20347E-5 1,39847 1,38476 4,41E-6 9,36604E-5 1,39979 1,38428 4,41E-6 9,5248E-5 1,39921 1,38808 4,41E-6 9,67988E-5 1,40167 1,38854 4,41E-6 9,83143E-5 1,4077 1,386828
Mass spectrometry data
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HP-IR data
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Catalyst characterization
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Figure S10. NOESY spectrum of phosphine 1 (1.0 μM) with porphyrin 2 (3.0 μM) in presence of viologen (3.0 μM) after addition of Rh(acac)(CO)2 (1.0 μM),
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2D
1H-DOSY spectra
All DOSY spectra were recorded using CD2Cl2:CD3CN=4:1 at 298 K. All individual components have a logD value of between 8.7 and
8.9 (see figure S11-14). When phosphine 1 is added to a solution of porphyrin 2 in presence of viologen and Rh(acac)(CO)2 a logD
value of 9.2 is obtained, indicating the species formed in solution is significantly larger than it’s individual components.
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Figure S15. DOSY spectrum of phosphine 1 (1.0 μM) with porphyrin 2 (3.0 μM) in presence of viologen (3.0 μM) after addition of Rh(acac)(CO)2 (1.0 μM), peaks
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IR initial rate data
Figure S16. Aldehyde yield as monitored by HP-IR, after ~20% conversion, the absorption of the aldehyde peak is too intense to follow accurately, final points
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Catalyst stability
To assess the stability of the encapsulated catalyst, the CO frequencies of the active complex are shown below, before and after the addition, and full conversion, of 800 equivalents of 1-octene. Both frequency and the intensity remain virtually identical.
Figure S19. Comparison of the CO-stretching frequency bands before (top) and after (bottom) catalysis, showing that the complex doesn’t change significantly
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Selectivity determination
To confirm the use of GC methods as a reliable way of determining the selectivity for the linear and branched product in the hydroformylation of 1-octene the GC method was confirmed using 1H-NMR in the following was: under inert conditions an autoclave
was loaded with Rh(acac)(CO)2 (4.0 μmol), phosphine 1 (10.0 μmol), Zinc tetraphenylporphyrin (30.0 μmol) and 1-octene (3200 μmol)
in 4 ml DCM:MeCN, pressurized with syngas to 20 bar and stirred at 25°C for 1h. After this time the pressure was released and 50 μL of the mixture was diluted with 1450 μL DCM and examined with GC (see figure S20 below). 300 μL of the reaction mixture was diluted with 300 μLCDCl3 and a 1H-NMR was taken (see S21 below). The obtained linear to branched ratios were found to be
identical.
Figure S20. GC chromatogram of an encapsulated hydroformylation catalyst after reaction with 1-octene, 1-octene observed after 4.3 minutes, n-decane
observed after 7.7 minutes, branched product observed after 8.5 minutes, linear product observed after 9.1 minute, linear/branched ratio=0.63, for comparison to the l/b ratio (figure S21, vide infra).
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Figure S21. Linear to branched ratio as determined with NMR for comparison to the GC data of the same reactions (S20, vide supra), linear product observed at
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Additional catalytic experiments
Additional control experiments were performed to show the effect of viologen and porphyrin 2 on the catalysis in absence of phosphine 1. The results show that the conversion is low in all cases and the l/b selectivity is similar.
Table S1. Control experiments performed in absence of phosphine 1
Conditions: [Rh(acac)(CO)2]=1.0 mM, T=25 °C, t=24h, p=20 bar (CO:H2=1:1), solvent: dichloromethane:acetonitrile = 4:1, porphyrin:Rh=7.5:1,
cofactor:Rh=8.25:1; substrate:Rh=800:1 [a] Yield of aldehyde products, determined with GC with decane as an internal standard
Ligand Cofactor Yield[a] l/b ratio[a]
Rh(acac)(CO)2 - >1% 1.17
Rh(acac)(CO)2 viologen 3.5% 1.25
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XYZ coordinate file of the xTB calculations
ZN 5.27429516641791 9.74014612888849 4.89096643602340 O 6.63180730762229 7.79056358871801 0.13388676213077 O 9.66484169647878 8.16527990030016 0.49938582731232 O 9.90294495501117 10.66543406722229 1.76586777102345 O 8.52704295218545 13.82720259081036 2.73489526262783 O 14.27486878299972 10.29088865228216 4.56063969090621 O 13.48275499637722 5.73179275432645 2.46606263731558 O 10.25335261614865 5.97190044563457 6.55657463438468 O 7.34530735594087 5.27704738960508 7.13385433788470 O 10.80351968168690 8.44427529102320 7.81943771195513 O 9.10830469875736 10.51663718155186 8.95065476617503 N 5.20135491383074 10.39142843653880 2.95800155522661 N 6.08869190237716 11.53168310667359 5.44354176113917 N 5.82341850268080 8.97525508762041 6.71552151278356 N 4.93517177423898 7.83578533298160 4.23392004270985 N 15.38842919639032 9.37084898947509 2.76926775305466 N 15.68469300591633 8.47946622756356 4.76574467396695 N 15.24677598076649 6.34361919355416 3.80904002040216 N 15.11090102011770 7.21551554527766 1.78803281452306 C 5.38429871048288 11.67065842714882 2.53168581737449 C 5.85099140607103 12.72801343273635 3.31127873231185 C 6.18247169455822 12.64326169528418 4.66604818987706 C 6.52382173464526 11.88037532094189 6.68617817984412 C 6.59458407064729 11.03872390033520 7.79769368211961 C 6.24323064654335 9.68887206810781 7.79695024380962 C 5.57940504499739 7.70869499572776 7.15278576756905 C 5.14896564812967 6.64017590158677 6.36620972444045 C 4.88344494113403 6.71228160508941 4.99974284072406 C 4.64726903265873 7.45607308100066 2.95877229657288 C 4.59735707562094 8.29221469488281 1.84615607045908 C 4.84209304907585 9.66278780632311 1.86694761233925 C 4.77447741720462 10.51473512940031 0.71024604044746 C 5.11339843562601 11.75990820257616 1.12071928259862 H 5.17742305842445 12.65751564923676 0.53614285726462 C 4.31884140527681 7.66265794602815 0.53186556881975 C 5.39076877286654 7.44507607347771 -0.34502079760911 C 7.64482404544870 8.11010528378427 -0.79768358974069 H 7.21743613972475 8.65725531838747 -1.64514904171256 H 8.13913513460705 7.20290002665034 -1.16866474181775 C 8.67443631791734 8.99286007766175 -0.09364092061659 H 9.14333295615567 9.66285833494254 -0.82169738334869 H 8.16181575738363 9.58875157762527 0.66955616998694 C 10.88344883254520 8.74477430728375 0.77208224961563 C 11.04079759952340 10.00164632021387 1.38047157929013 C 9.98532680130616 12.03601721729993 2.09769806438652 O 1.88724301476945 15.34138086682279 0.55099036743391 C 0.70401167622986 10.88493677773045 1.59752102665459 C 8.54793369599249 12.45989077074380 2.39486716575592 H 0.34445182586243 24.55644639949127 5.19236081823421 C 7.37963702346321 14.53537777795238 2.45587148746288 C 6.08548955619083 14.04033556424526 2.66014078056728 C 5.00132604352608 14.83396327084271 2.30095994508902 H 4.00509349068040 14.43272097361928 2.43309963671376 C 5.17704445068312 16.10848963392564 1.79720620010961 H 4.31993496589430 16.70424878213884 1.52338671872279 C 6.45908785112648 16.61399421015230 1.65612508252694 H 6.60794089810368 17.61297626966543 1.27787676830322 C 7.55105473437042 15.82873830678702 1.97195528205248 H 8.55682517651206 16.19642156809830 1.84368221987143 C 12.32324437021732 10.47347807745174 1.62512686548860 H 12.46350064441234 11.44247342461652 2.07554842423122 C 13.44579785561459 9.71271248678831 1.33792279648035 C 14.81296202944654 10.20853488752453 1.74086555310685 H 15.49948414857413 10.21297844706859 0.88980303291313 H 14.74128188810828 11.21993342820682 2.14665954065139 C 15.02789798048910 9.45995589311873 4.08057143368935 C 16.18762569945058 7.44704414548441 3.87902560423198 C 14.49889235433620 6.37070027582668 2.67115981546796
29
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