a self-catalyzed reaction of 1,2-dibenzoyl o …chemical communications supporting information a...
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Chemical Communications
Supporting Information
A Self-Catalyzed Reaction of 1,2-Dibenzoyl o-Carborane
with Hydrosilanes – Formation of New Hydrofuranes †
Kuldeep Jaiswal,a Solomon Volodarsky,a Vladimir Kampel,a and Roman
Dobrovetsky*a
Electronic Supplementary Material (ESI) for ChemComm.This journal is © The Royal Society of Chemistry 2019
General experimental considerations
Commercial reagents were purchased from Sigma Aldrich, Strem or Apollo Scientific and used
without further purification unless indicated otherwise. NMR spectra were recorded at room
temperature using a Bruker AvanceIII-400 MHz spectrometer. Data for 1H NMR are reported as
follows: chemical shift (δ ppm), integration, multiplicity (s = singlet, d = doublet, t = triplet, q =
quartet, quin = quintet, m = multiplet, br = broad), coupling constant (Hz), assignment.
1
Ortho-carborane (2) (2.00 gr, 13.87 mmol, 1 eq.) dissolved in 100 mL of Et2O, was
treated with n-BuLi (11.30 mL, 30.51 mmol, 2.20 eq.) at 0 °C. After 30 min benzoyl
chloride (3.30 mL, 28.43 mmol, 2.05 eq.) in 20 mL was added to the stirring
solution at −78 °C. The solution was allowed to rich r.t. and left to stir for additional
30 min at r.t., and then was heated to reflux for additional 30 min. The organic phase
was washed with water and then brine, separated, dried over Na2SO4. The solvent was evaporated
and a mixture of oil and crystals was obtained. The crude was recrystallized from hexane to give
pure 1 (3.50 gr, 9.93 mmol) as a red solid in 73% yield. 1H NMR (400 MHz; CDCl3), δ1.75-3.57
(10H, br, B-H), 7.46 (4H, t, J = 7.7 Hz), 7.59 (2H, t, J = 7.4 Hz), 7.86 (4H, d, J = 7.7 Hz). 13C NMR
(100 MHz; CDCl3), δ 84.1, 128.3, 129.4, 133.1, 135.3, 185.5. 11B{1H} NMR (128 MHz; CDCl3),
δ 1.16, 7.98, 10.64. HRMS (ESI+): m/z calc’d for C16H20B10O2 : 376.2328 (M + Na+); found:
376.2330.
3
1,2-Dibenzoyl ortho-Carborane (1) (150 mg, 426 µmol, 1 eq.) and Et3SiH (98 mg,
852 µmol, 2 eq.) were dissolved in o-difluorobenzene, and heated at 140 °C for 96h.
o-difluorobenzene was evaporated and 3 was crystalized from hexane (170 mg, 363
µmol) in 85% yield.
1H NMR (400 MHz; C6D6), δ 0.42-0.59 (6H, overlapped quartet, J = 7.98 Hz), 0.87 (9H, t, J = 7.98
Hz), 1.96-3.77 (10H, br, B-H), 5.38 (1H, s), 7.07-7.19 (7H, m), 7.34-7.36 (3H, m). 13C NMR (100
MHz; CDCl3), δ 6.1, 6.9, 82.4, 84.4, 87.6, 106.5, 126.3, 129.5, 129.7, 135.6, 140.8. 11B{1H} NMR
(128 MHz; C6D6), δ 5.22, 6.19, 6.98, 8.96, 10.38, 12.39, 14.45. HRMS (ASAP+): m/z calc’d for
C2oH31B10O2Si: 440.3060 (M - Et+); found: 440.3064.
4
1,2-Dibenzoyl ortho-Carborane (1) (150 mg, 426 µmol, 1 eq.) and PhSiH3 (82.8
mg, 767 µmol, 1.8 eq.) were dissolved in o-difluorobenzene, and heated at 140 °C
for 48h. o-difluorobenzene was evaporated and 4 was crystalized from hexane (150
mg, 340 µmol) in 80% yield.
1H NMR (400 MHz; C6D6), δ 1.78-3.46 (13H, br, B-H), 5.21 (2H, s), 7.10-7.13 (8H, m), 7.33-
7.34 (4H, m). 13C NMR (100 MHz; CDCl3), δ 83.2, 126.0, 129.5, 130.7, 133.7, 135.0. 11B{1H}
NMR (128 MHz; C6D6), δ 5.50, 6.44, 7.58, 8.51, 9.55, 11.20, 12.76, 13.86. HRMS (ASAP+): m/z
calc’d for C16H21B10O: 337.2596 (M - H-); found: 337.2591
A solution of bromopentafluorobenzene (7.41 g, 30 mmol) in THF (100 mL) was
added dropwise to magnesium turnings (0.95 g, 39 mmol) in THF (50 mL) at 0 °C.
The mixture was stirred at room temperature for 1 h. Anhydrous copper(I) iodide
(11.43 g, 60 mmol) was added to the resulting dark brown solution, and the mixture
was stirred at room temperature for 1 h. After addition of dioxane (30 mL), the resulting suspension
was stirred at room temperature for 1 h. Phthaloyl dichloride (3.05 g, 30 mmol) was added to the
suspension at 0 °C, and stirred continue at room temperature overnight. The resulting suspension
was filtered through Celite, washed with CHCl3, and evaporated under reduced pressure. The
residue was dissolved in CHCl3, and the solution was passed through silica gel. After removal of
the solvent, the residue was purified by column chromatography on silica gel with n-
hexane/ethylacetate to give white crystalline product (1.05g, 15%). 1H NMR (400 MHz; CDCl3), δ
7.61-7.63 (4H, m), 7.73-7.75. (4H, m). 13C NMR (100 MHz; CDCl3), δ
113.4,130.3,133.2,136.4,138.8,138.9,142.0,143.6,144.6,146.1,186.1. 19F NMR (400 MHz, CDCl3)
δ 139.8 (4F, dd, J = 17.4, 8.7 Hz,), 148.3 (2F, t, J = 20.2 Hz), 160.3 (4F, dt, J = 20.2, 5.7 Hz),
HRMS (ASAP+): m/z calc’d for C20H4F10O2: 467.0130 (M + H+); found: 467.0128.
Figure.S1 Molecular structure of C6H4(CO(C6F5))2 (1941243).
Figure S2. 1H NMR of 1
Figure S3. 1H{11B} NMR of 1
Figure S4. 13C NMR of 1
Figure S5. 11B NMR of 1
Figure S6. 11B{1H} NMR of 1
Figure S7. 1H NMR of 3
Figure S8. 1H{11B} NMR of 3
Figure S9. 13C NMR of 3
Figure S10. 11B NMR of 3
Figure S11. 11B{1H} NMR of 3
Figure S12. 1H NMR of 4
Figure S13. 13C NMR of 4
Figure S14. 11B NMR of 4
Figure S15. 11B{1H} NMR of 4
Figure S16. 19F NMR; Reaction of 1 with [Bu4NH][B(C6F5)4]
Figure S17. 11B NMR; Reaction of 1 with Bu4NHB(C6F5)4
Figure S18. 19F NMR; Reaction of 1 with B(C6F5)3
Figure S19. 11B NMR; Reaction of 1 with B(C6F5)3
Figure S20. 1H NMR of C6H4(CO(C6F5))2
Figure S21. 13C NMR of C6H4(CO(C6F5))2
Figure S22. 19F NMR of C6H4(CO(C6F5))2
Figure S23. 1H NMR; Reaction of C6H4(CO(C6F5))2 with Et3SiH
Figure S24. 13C NMR; Reaction of C6H4(CO(C6F5))2 with Et3SiH
DFT calculations
DFT calculations were performed using Gaussian 09.2.1 Geometry optimization of all the
molecules, intermediates, and the transition state were carried out using the ωB97XD/def2-SVP
basis sets2 in 1,2-dichlorobenzene using the polarizable continuum model (PCM)3 implemented in
the Gaussian 09 software. Thermal energy corrections were extracted from the results of frequency
analysis performed at the same level of theory. Frequency analysis of all the molecules and
intermediates contained no imaginary frequency showing that these are energy minima. The
transition states geometries gave one imaginary frequency at expected reaction coordinates
confirming that it is a first-order saddle point.
1:
C 2.58508000 -1.71842000 -0.89348100
H 1.59752800 -1.89380100 -1.31709500
C 3.71630900 -2.25120400 -1.50824900
H 3.60749700 -2.82372200 -2.43141600
C 4.97933000 -2.05888200 -0.94851000
H 5.86301200 -2.47202700 -1.43918900
C 5.11161500 -1.34906500 0.24496300
H 6.09655500 -1.20328700 0.69270600
C 3.98324200 -0.82917100 0.87378200
H 4.08087400 -0.28010100 1.81271300
C 2.71759800 -0.99670300 0.29700800
C 1.56442000 -0.40818100 1.04908900
O 1.34313900 -0.70070200 2.19357100
C 0.80621000 0.79793300 0.42574300
B 1.67870700 2.00261100 -0.40574600
H 2.84664600 1.81726400 -0.57926300
B 1.05053100 2.27492500 1.23698700
H 1.79993700 2.27108400 2.16798000
B 0.51489900 2.68786700 -1.56273500
H 0.86538000 3.10391700 -2.63086900
B 0.83497400 3.51849200 -0.01492700
H 1.43809200 4.55417100 0.03958000
B -0.49939600 3.14037900 1.10862400
H -0.87255200 3.88502700 1.97069800
B -0.48883200 1.39601400 1.41182500
H -0.80263500 0.76349700 2.36966100
B -0.82975100 3.39615000 -0.62711400
H -1.45417100 4.33919400 -1.02705700
B -1.64190300 2.08582100 0.25365100
H -2.80136700 1.96603300 0.50668300
B -1.01711300 1.79920100 -1.38889000
H -1.73550900 1.47683700 -2.28688900
B 0.54288600 0.94784800 -1.26248900
H 0.83857400 0.05295000 -1.98526600
C -1.27919000 -0.75976600 -0.10551000
C -0.74416700 0.68066300 -0.13187800
O -0.46339500 -1.64926900 -0.02052600
C -2.73615800 -1.05156600 -0.10142800
C -3.70514900 -0.28160000 -0.75990700
H -3.42654300 0.60655100 -1.32288300
C -5.04135700 -0.67141000 -0.72863600
H -5.78821700 -0.07467600 -1.25498500
C -5.42304800 -1.81613600 -0.02949700
H -6.47449200 -2.10929300 0.00233200
C -4.46303300 -2.58927700 0.62570100
H -4.75882300 -3.48687100 1.17171000
C -3.12483000 -2.21746600 0.57922500
H -2.36398900 -2.81800600 1.08007900
Sum of electronic and zero-point Energies= -1019.470325
Sum of electronic and thermal Energies= -1019.449844
Sum of electronic and thermal Enthalpies= -1019.448900
Sum of electronic and thermal Free Energies= -1019.519030
:
H 0.00000400 0.00033500 1.87766000
Si 0.00004700 -0.00011900 0.37612000
C 1.78441500 -0.02330700 -0.22194300
H 2.33507200 0.86044500 0.13699500
H 2.31152900 -0.92133500 0.13662000
H 1.82368300 -0.02357500 -1.32321200
C -0.87204900 1.55685900 -0.22201300
H -0.88601300 1.59468300 -1.32322400
H -1.91434100 1.58852200 0.13219100
H -0.36111700 2.46201100 0.14220800
C -0.91251500 -1.53359200 -0.22194200
H -0.42422200 -2.45227600 0.13933700
H -1.95457800 -1.53817400 0.13430400
H -0.92977500 -1.56873200 -1.32317000
Sum of electronic and zero-point Energies= -409.530519
Sum of electronic and thermal Energies= -409.522887
Sum of electronic and thermal Enthalpies= -409.521942
Sum of electronic and thermal Free Energies= -409.561107
π-stacking:
C -1.39516800 2.94835200 1.37408000
H -0.64924900 2.45394700 1.99800700
C -1.62963500 4.31311700 1.50724900
H -1.07027500 4.88908200 2.24648000
C -2.56673200 4.94147700 0.68787600
H -2.74440000 6.01418100 0.78753900
C -3.26934500 4.20628300 -0.26724800
H -3.98441200 4.70301900 -0.92520600
C -3.06332100 2.83525500 -0.38513200
H -3.61045800 2.26708000 -1.13803000
C -2.12789700 2.20258400 0.44174200
C -1.83533900 0.75027900 0.35734100
O -0.70956400 0.31962500 0.28854900
C -2.98311900 -0.26001900 0.49739500
B -3.68340300 -0.47551500 2.04081300
H -3.32828000 0.26392400 2.91153800
B -4.63836800 0.14472400 0.68016400
H -4.95092100 1.29431500 0.65726200
B -4.03181200 -0.59719300 -0.81009900
H -3.85817600 -0.02697400 -1.83857700
B -5.50880400 -1.20976800 -0.06332900
H -6.55508300 -1.04565100 -0.62478800
B -5.30716300 -1.13266000 1.70992200
H -6.22300200 -0.89529200 2.44727600
B -5.11022700 -2.68110400 0.86096400
H -5.88186000 -3.59327600 0.96756800
B -4.29420400 -2.35796900 -0.69251300
H -4.35061000 -2.97999700 -1.71240100
B -3.37470200 -2.99611100 0.68730800
H -2.83802300 -4.05663000 0.59352500
B -3.98163900 -2.23025400 2.17129700
H -3.92309100 -2.78882300 3.23031900
B -2.49228500 -1.65145400 1.42912000
H -1.37207300 -1.66534400 1.82592800
C -2.78100700 -1.69952000 -0.26052900
C -1.63519800 -1.83818200 -1.29629900
O -1.56585200 -1.01688600 -2.17727900
C -0.75860000 -3.04159400 -1.28585900
C -0.26389100 -3.65725300 -0.12849800
H -0.48353700 -3.25146400 0.85625700
C 0.54604500 -4.78409700 -0.23023500
H 0.93805700 -5.24899700 0.67585000
C 0.85786100 -5.31375900 -1.48170500
H 1.48281700 -6.20604400 -1.55555200
C 0.38597900 -4.69464600 -2.63924800
H 0.63677700 -5.10047200 -3.62085300
C -0.40702400 -3.55652700 -2.54311300
H -0.78056900 -3.06455500 -3.44258600
C 1.45451700 0.16610500 2.82538500
H 0.84283100 0.49043200 1.98630900
C 0.84167200 -0.35894500 3.96058800
H -0.24627300 -0.44996000 3.99054700
C 1.60916600 -0.76258600 5.05358500
H 1.12466500 -1.18280800 5.93735000
C 2.99609300 -0.62051300 5.01801100
H 3.60271100 -0.92863700 5.87187100
C 3.61171800 -0.07726000 3.89288700
H 4.69617300 0.04645600 3.86543100
C 2.84693500 0.30356700 2.78210200
C 3.61112100 0.88591400 1.63040100
O 4.45160300 1.72856700 1.80627800
C 3.54370600 0.20735200 0.23136500
B 3.95905200 -1.43743900 0.12150300
H 4.17517400 -2.01550900 1.14671300
B 5.07163000 -0.17134800 -0.44301000
H 6.04034200 0.10194700 0.19959500
B 3.05942200 -2.04463400 -1.28544500
H 2.65581100 -3.16942700 -1.33398000
B 4.77733400 -1.59897300 -1.45169300
H 5.63513500 -2.42360000 -1.60965900
B 4.86090900 0.02014200 -2.19748000
H 5.76184800 0.38771000 -2.89854300
B 4.10644600 1.17003400 -1.08630400
H 4.31930900 2.32441400 -0.88557300
B 3.61648500 -1.14567700 -2.71927900
H 3.61550000 -1.63443300 -3.81548900
B 3.19370600 0.56401500 -2.49093400
H 2.84095700 1.36629100 -3.30326100
B 2.08620600 -0.70840600 -1.92971000
H 0.98500400 -0.83510200 -2.36027900
B 2.29317400 -0.90360000 -0.17801200
H 1.39102100 -1.07941000 0.56866700
C 1.56925000 1.81485400 -0.52796200
C 2.46654200 0.63688100 -0.94589700
O 1.70391500 2.22931800 0.60097500
C 0.69503400 2.51547100 -1.50229000
C 0.04207000 1.89411500 -2.57395400
H 0.15209800 0.82755500 -2.74909800
C -0.80250300 2.63464000 -3.39595500
H -1.32171700 2.13903600 -4.21826800
C -0.98510400 3.99831700 -3.17041500
H -1.64219600 4.57681300 -3.82319300
C -0.33613300 4.62332700 -2.10501300
H -0.48419700 5.68852300 -1.91960300
C 0.48981600 3.88380200 -1.26778300
H 0.98750400 4.35790800 -0.42092900
Sum of electronic and zero-point Energies= -2038.969160
Sum of electronic and thermal Energies= -2038.926690
Sum of electronic and thermal Enthalpies= -2038.925746
Sum of electronic and thermal Free Energies= -2039.042697
TS1:
O 1.49669100 -0.03755700 -1.28536400
C 5.78770300 -1.97206800 -2.87474800
H 6.65128400 -2.26820900 -3.47468400
C 5.62647900 -2.47011300 -1.58211700
H 6.36495900 -3.15653100 -1.16177000
C 4.52312500 -2.09209200 -0.81797700
H 4.43014700 -2.47989300 0.19415900
C 3.56086900 -1.21813500 -1.33102600
C 3.73891800 -0.71615600 -2.62256100
H 2.98599000 -0.02760100 -3.00618500
C 4.84078300 -1.08702700 -3.39004500
H 4.96164600 -0.68060500 -4.39696200
C 2.27768700 -0.77525900 -0.59844000
H 1.73332300 -1.85786700 -0.26889500
C 2.52460700 -0.19791700 0.86985800
C 2.67359100 1.43044200 0.92404100
C 2.79718500 2.23631200 -0.38784400
B 2.60018500 -0.31799500 3.64424400
H 2.57058000 -1.00293200 4.63106200
B 3.38850700 -0.91014900 2.16548600
H 3.87690600 -1.99001600 2.02729800
B 1.63509900 -0.73944000 2.21557000
H 0.96872400 -1.71210900 2.05935800
B 1.22978200 0.70880700 3.15901500
H 0.20308800 0.78604800 3.77741800
B 2.76639400 1.45045700 3.68247600
H 2.85970700 2.08285500 4.69949100
B 4.10551100 0.44374800 3.06562100
H 5.16259800 0.33096600 3.62302800
B 1.17375800 0.75470300 1.39326500
H 0.24555500 0.86553400 0.66681300
B 1.88715200 2.10467700 2.28682600
H 1.38265000 3.18170400 2.16715800
B 3.65576800 1.94270700 2.22216100
H 4.33682900 2.91227400 2.05201000
B 4.05640500 0.47629300 1.30009500
H 4.94184900 0.42786600 0.51005300
O 3.79493900 2.14548000 -1.05244700
C 1.75854500 3.27959900 -0.67279000
C 0.54931800 2.97179500 -1.29825600
C 2.07264100 4.60666400 -0.35780100
C -0.33820900 3.99908500 -1.61349100
H 0.33644300 1.93118600 -1.54273600
C 1.16837500 5.62361500 -0.65463300
H 3.02426000 4.84105900 0.12504100
C -0.03719800 5.31994000 -1.28690900
H -1.27700700 3.76575100 -2.11682000
H 1.41048000 6.65739800 -0.39961300
H -0.74606700 6.11506500 -1.52666800
O -2.24878900 0.33796800 1.39145500
C -2.39695100 5.29038200 1.22439300
H -2.29490400 6.36094500 1.41336600
C -3.32262900 4.83416800 0.28716300
H -3.95563500 5.54247100 -0.24990200
C -3.44089200 3.47330500 0.02218400
H -4.17396000 3.14393400 -0.70920100
C -2.64011600 2.55154700 0.71166200
C -1.72964800 3.02013900 1.67494500
H -1.11874500 2.30138900 2.22029600
C -1.59943700 4.38042900 1.91915700
H -0.87193900 4.73182700 2.65282900
C -2.67695200 1.07832700 0.53479900
C -3.16420600 0.41245700 -0.76175300
C -2.76615300 -1.20083000 -0.85679200
C -1.90950400 -1.86449000 0.24856200
B -4.35924200 0.32072900 -3.24877700
H -4.95253600 0.90427800 -4.11240900
B -3.10533500 1.14141100 -2.29995300
H -2.75584600 2.27739900 -2.36857700
B -4.65221100 0.70534300 -1.53755300
H -5.38775900 1.52161200 -1.07271500
B -5.16330700 -0.86781000 -2.18439100
H -6.32541500 -1.14783500 -2.26992700
B -3.91993800 -1.39452200 -3.35765500
H -4.18869900 -2.08844100 -4.29826900
B -2.64420600 -0.14998400 -3.41907100
H -1.98749100 0.08057400 -4.39449900
B -4.40827500 -0.77772700 -0.58505800
H -4.86461200 -0.92802700 0.50355400
B -3.94707700 -2.07433700 -1.72055600
H -4.14637100 -3.21435600 -1.43331200
B -2.40058600 -1.62866300 -2.46768900
H -1.56485700 -2.46284500 -2.64084600
B -1.88321700 -0.05862900 -1.82156900
H -0.76576500 0.17349500 -1.49047900
O -0.70801800 -1.89696800 0.04985700
Si 0.92232200 -3.56500600 -0.59298500
C 2.18582300 -4.27333100 0.58177200
H 3.21402000 -4.09930900 0.24591300
H 2.06198200 -3.84129500 1.58622800
H 2.00846100 -5.35785500 0.65820600
C -0.60965100 -4.61371400 -0.39511700
H -0.94549800 -4.69636200 0.64810000
H -1.44782300 -4.30115700 -1.03252300
H -0.29203700 -5.61849400 -0.72674800
C 1.25860900 -3.21820700 -2.38503900
H 0.99941900 -2.16852100 -2.60416400
H 2.32273300 -3.35737300 -2.62061600
H 0.64437300 -3.87960700 -3.01326900
C -2.50472700 -2.52725300 1.44119700
C -1.75925400 -2.45580500 2.62797500
C -3.69824400 -3.26048200 1.43051100
C -2.20029000 -3.09324200 3.78023100
H -0.84471800 -1.86646800 2.64474800
C -4.12656800 -3.91637100 2.58251200
H -4.29027700 -3.35815000 0.52471100
C -3.38469200 -3.83184700 3.75881200
H -1.61916000 -3.01065700 4.70040900
H -5.05055900 -4.49658700 2.55568700
H -3.73088200 -4.33912500 4.66156400
Sum of electronic and zero-point Energies= -2448.436876
Sum of electronic and thermal Energies= -2448.387233
Sum of electronic and thermal Enthalpies= -2448.386289
Sum of electronic and thermal Free Energies= -2448.516296
5:
O 4.41901500 -1.22904700 1.00181500
C 7.11202900 -2.63431900 -3.05724300
H 7.52224900 -3.14187600 -3.93335100
C 7.91207800 -1.76407600 -2.31580300
H 8.95095100 -1.59070200 -2.60533900
C 7.38600800 -1.12040000 -1.19646900
H 8.01633800 -0.44464700 -0.61097300
C 6.05817800 -1.33398700 -0.81652500
C 5.26018400 -2.21014700 -1.55544000
H 4.21985500 -2.34473300 -1.24531500
C 5.78834200 -2.85602200 -2.67321600
H 5.15980300 -3.53616600 -3.25308600
C 5.50394300 -0.60193800 0.39082900
H 6.31440700 -0.51642700 1.13459400
C 5.04004500 0.84352000 0.08288700
C 3.47894700 0.85897500 0.38575800
C 3.05419300 -0.66925900 0.70141500
B 5.07989100 3.53377300 -0.46987300
H 5.69573200 4.51353000 -0.79598200
B 5.47843300 1.93647300 -1.14903700
H 6.37228000 1.65351600 -1.89332400
B 5.81658300 2.28803500 0.55952300
H 6.93929600 2.22205700 0.97309600
B 4.49196000 3.30393500 1.19577000
H 4.67835200 4.09321600 2.08233100
B 3.32648900 3.55920500 -0.12675600
H 2.66135400 4.55947900 -0.20233100
B 3.93792000 2.73504100 -1.58155400
H 3.72705000 3.12469400 -2.69845100
B 4.52782800 1.58313700 1.54149400
H 4.73694300 1.00231100 2.55990400
B 2.99653500 2.32913200 1.11292400
H 2.11593000 2.31380400 1.92391700
B 2.65451300 1.97607000 -0.59115900
H 1.53547000 1.73680600 -0.94036400
B 3.97364800 1.01020100 -1.25587800
H 3.82910000 0.08512000 -1.98507000
O 2.45436400 -1.24656900 -0.27168400
C 2.28750500 -0.68927800 2.03547300
C 2.87542300 -0.94629600 3.27485000
C 0.91719400 -0.41327000 1.98802600
C 2.11141200 -0.91419600 4.44435400
H 3.94049800 -1.17558300 3.31475500
C 0.15506600 -0.36192600 3.15150100
H 0.45363700 -0.26088200 1.01106600
C 0.75165000 -0.61252900 4.38904000
H 2.58582900 -1.12293100 5.40633600
H -0.91093200 -0.13434100 3.09337100
H 0.15662700 -0.57889600 5.30472600
O -2.60931400 0.24775000 0.17160200
C -1.12994400 4.97296800 0.57310400
H -0.59274800 5.90800700 0.74337800
C -2.46013700 5.00932300 0.14716200
H -2.96173400 5.96419600 -0.01106600
C -3.14255000 3.82639300 -0.07843500
H -4.17812100 3.86470300 -0.40764900
C -2.49349700 2.58651000 0.13072800
C -1.14455600 2.56326300 0.56774700
H -0.61219900 1.62293600 0.71595400
C -0.47472600 3.75434600 0.78076200
H 0.56630600 3.73856500 1.10188700
C -3.17161500 1.35569200 -0.10224700
C -4.54044400 1.16686400 -0.68066000
C -4.68760200 -0.42561600 -0.76793000
C -3.36411600 -1.06191600 -0.27352200
B -7.03993800 1.54655800 -1.73517700
H -7.90081400 2.30186800 -2.08622900
B -5.32810800 1.96774200 -1.96915500
H -4.84281600 2.96794800 -2.40324000
B -6.02887200 1.93395900 -0.32513100
H -6.02168000 2.90900200 0.36302700
B -7.18977300 0.57795500 -0.24279300
H -8.13670800 0.62759900 0.48778300
B -7.19276100 -0.23057200 -1.83681100
H -8.17175800 -0.77176000 -2.26563200
B -6.05286300 0.63180300 -2.90849900
H -6.18819400 0.71938400 -4.09477300
B -5.59517300 0.38994900 0.45723100
H -5.20700600 0.31483100 1.57844100
B -6.27792500 -0.94632300 -0.48894100
H -6.44021100 -1.98970500 0.06839600
B -5.57317600 -0.91317300 -2.12906300
H -5.27062600 -1.93499300 -2.66589400
B -4.43805200 0.45074300 -2.25741500
H -3.35788800 0.40379300 -2.75234400
O -2.70456100 -1.59380400 -1.27727500
Si -1.01587600 -2.06079000 -1.48793800
C -0.38278300 -2.86879300 0.06335100
H -0.77794800 -2.40392400 0.97750700
H -0.62678700 -3.94130900 0.08975000
H 0.71081300 -2.71425400 0.07206600
C -1.13394100 -3.23889300 -2.92370300
H -1.73020000 -4.12539500 -2.65899600
H -1.58992500 -2.75483600 -3.80035500
H -0.12419300 -3.57760400 -3.20503400
C -0.13832600 -0.47650300 -1.91280200
H -0.48493900 0.35220200 -1.27845000
H 0.93526900 -0.61295400 -1.69490600
H -0.29392700 -0.19053600 -2.96377000
C -3.46687400 -1.93262600 0.95901900
C -3.30879400 -1.44637800 2.25692400
C -3.72448400 -3.29029800 0.74772000
C -3.39131400 -2.31835100 3.34041500
H -3.10280300 -0.39049800 2.43160800
C -3.81926000 -4.15563900 1.83349100
H -3.83770900 -3.67276300 -0.26838900
C -3.64699700 -3.67203900 3.13065100
H -3.24784500 -1.93450900 4.35191800
H -4.01744900 -5.21529700 1.66392700
H -3.70792100 -4.35479900 3.98026700
Sum of electronic and zero-point Energies= -2448.489278
Sum of electronic and thermal Energies= -2448.440479
Sum of electronic and thermal Enthalpies= -2448.439535
Sum of electronic and thermal Free Energies= -2448.569670
TS2:
O 4.17150800 -1.41857800 0.78583200
C 5.19769100 -3.25520200 -3.80807600
H 5.21749700 -3.82218100 -4.73571600
C 6.30952100 -2.49497900 -3.42977000
H 7.19544100 -2.47015300 -4.06156800
C 6.28535900 -1.77217100 -2.23461100
H 7.15260700 -1.17478500 -1.93980500
C 5.14883600 -1.79600900 -1.41615600
C 4.03912600 -2.55292100 -1.79213300
H 3.16369000 -2.54432200 -1.14398100
C 4.06625800 -3.28761600 -2.98617600
H 3.20144000 -3.87889300 -3.27613800
C 5.13437300 -0.99034500 -0.13650800
H 6.11619000 -1.08427400 0.34933700
C 4.88292300 0.52797200 -0.33014100
C 3.49828500 0.82032100 0.39328200
C 2.92053300 -0.62100700 0.85969700
B 5.26590900 3.17124100 -0.95177700
H 5.93224300 4.02605900 -1.46738400
B 5.15349900 1.54299100 -1.66935700
H 5.73951000 1.11875200 -2.62209100
B 6.01474600 1.79179100 -0.12974500
H 7.17350500 1.50986900 -0.03649600
B 5.12591700 3.01999400 0.81057700
H 5.68901900 3.74082200 1.59611600
B 3.70824500 3.51274300 -0.14125200
H 3.23053000 4.61698300 -0.06405500
B 3.73142700 2.62670000 -1.68426500
H 3.29134100 3.06891900 -2.70996600
B 4.93302700 1.31394100 1.19620900
H 5.29615300 0.67322000 2.12885800
B 3.51360900 2.34015400 1.17219000
H 2.89980400 2.48635300 2.19743600
B 2.65373000 2.09235600 -0.36046200
H 1.45893900 2.07215700 -0.37086900
B 3.54540500 0.91824700 -1.32963800
H 3.04839400 0.03940900 -1.95684300
O 1.96075700 -1.06062400 0.11956800
C 2.57163800 -0.53348500 2.36282200
C 3.32879700 -1.12086000 3.37114400
C 1.42018000 0.18946600 2.69849300
C 2.92532300 -1.00680900 4.71009900
H 4.22879000 -1.68055700 3.10708600
C 1.02855300 0.32001900 4.02860900
H 0.85591200 0.63825000 1.89048600
C 1.78062300 -0.28403600 5.04499000
H 3.52052100 -1.46921700 5.49795700
H 0.12605800 0.89187000 4.27459300
H 1.47690600 -0.18160200 6.08649100
O -2.70835900 0.32392700 0.59863600
C -0.57268300 4.73724800 0.84292700
H 0.11996500 5.56663900 0.99877900
C -1.71929100 4.92829000 0.07680300
H -1.94503900 5.90974200 -0.34899000
C -2.58459400 3.86438000 -0.15943500
H -3.47700400 4.01751100 -0.76854600
C -2.28757800 2.60061200 0.38444500
C -1.13481800 2.43089400 1.18995700
H -0.91978400 1.44483500 1.60699200
C -0.27376800 3.49704700 1.41090800
H 0.63993600 3.34426500 1.99226000
C -3.04433600 1.41357000 0.07692200
C -4.21184900 1.27686200 -0.85301200
C -4.46227400 -0.31535900 -0.94222100
C -3.36150700 -1.06793300 -0.15362300
B -6.36737600 1.80570900 -2.47181500
H -7.05483700 2.61341300 -3.02455100
B -4.61320000 2.08187700 -2.31248400
H -3.96518900 3.02244000 -2.64875800
B -5.67485400 2.16213900 -0.87404400
H -5.73088900 3.16076400 -0.21753200
B -6.92741200 0.90615800 -1.03661900
H -8.01435800 1.05411300 -0.54236700
B -6.64042400 0.03858500 -2.57476800
H -7.53532800 -0.43510900 -3.20658800
B -5.21508500 0.77439100 -3.36918800
H -5.06372600 0.82676100 -4.55488000
B -5.56074200 0.62239400 0.01015000
H -5.45030100 0.55870400 1.19326700
B -6.11378500 -0.69733300 -1.04097500
H -6.49448600 -1.69550000 -0.51460800
B -5.05251500 -0.77565600 -2.46167700
H -4.71764700 -1.83054900 -2.90889500
B -3.81728000 0.49970300 -2.34590900
H -2.66642100 0.34376600 -2.59122200
O -2.40621000 -1.54201700 -0.87967700
Si -0.56588100 -1.63617300 -0.51758700
C -0.59270900 -2.00367200 1.30818100
H -0.97440000 -1.18042400 1.93572900
H -1.22436000 -2.89601800 1.49333500
H 0.44043900 -2.20440000 1.59637900
C -0.07644300 -3.11311400 -1.52214900
H -0.55960000 -4.03615100 -1.16481600
H -0.30369100 -2.97977900 -2.58661600
H 1.01431900 -3.23633700 -1.41267100
C -0.15969600 -0.04224500 -1.40904400
H -0.35615300 0.85829900 -0.79557800
H 0.93874900 -0.06619400 -1.63820900
H -0.75383000 0.01167000 -2.36468900
C -3.84132900 -1.93510500 0.98555400
C -4.03930400 -1.48756800 2.29590400
C -4.09227300 -3.26800500 0.66304200
C -4.49046400 -2.37076800 3.26830000
H -3.80756200 -0.45896800 2.56358700
C -4.55339200 -4.14406900 1.63556200
H -3.91684100 -3.61761300 -0.35927200
C -4.75234100 -3.69633800 2.93502200
H -4.62536700 -2.02030600 4.29545500
H -4.75289000 -5.19415700 1.37953300
H -5.11585400 -4.39635000 3.70797500
Sum of electronic and zero-point Energies= -2448.481363
Sum of electronic and thermal Energies= -2448.433191
Sum of electronic and thermal Enthalpies= -2448.432246
Sum of electronic and thermal Free Energies= -2448.562866
3c:
O -0.07198200 -0.53143000 -1.05930300
C -4.63380900 -2.61384000 -0.59122100
H -5.47522900 -3.29000900 -0.42585300
C -4.80453900 -1.45750600 -1.35394700
H -5.77904300 -1.22682100 -1.78905500
C -3.72846700 -0.59939400 -1.57194600
H -3.86425200 0.30167200 -2.17623100
C -2.47750700 -0.88586700 -1.01825700
C -2.30947600 -2.04415800 -0.26035200
H -1.32921400 -2.26078400 0.16240800
C -3.38360700 -2.90656000 -0.04701600
H -3.24110500 -3.81269500 0.54561100
C -1.33474600 0.07778100 -1.24084600
H -1.38841600 0.45242100 -2.27500400
C -1.34074800 1.29994100 -0.30852600
C 0.08167800 1.29331700 0.41483000
C 0.80206700 0.00006800 -0.07761700
B -2.07951600 3.62750500 0.93093400
H -2.90066400 4.48513100 1.10818300
B -2.57163300 1.93668400 0.67913200
H -3.67358000 1.48261400 0.58521600
B -1.87663000 2.87401400 -0.66680300
H -2.50922200 3.04275200 -1.66863900
B -0.59318000 3.93134600 -0.00540800
H -0.33166000 4.98575900 -0.51411200
B -0.49025500 3.62189500 1.74812700
H -0.15086600 4.47440600 2.52230100
B -1.71649900 2.40373800 2.17896400
H -2.26309500 2.36395500 3.24611800
B -0.16674300 2.44631500 -0.83391700
H 0.35606700 2.23475400 -1.88407100
B 0.68988500 2.87437600 0.65026900
H 1.86753100 3.06166300 0.58840200
B 0.00033500 1.92465100 1.99107300
H 0.71897200 1.47209300 2.83223900
B -1.30886100 0.90610700 1.36696800
H -1.48169200 -0.22837800 1.67290400
O 0.91799400 -0.85415500 0.98777200
Si 1.59584100 -2.42558200 1.08958500
C 1.56706900 -3.25297600 -0.58686400
H 0.54879200 -3.31756000 -0.99654300
H 2.19148100 -2.70219500 -1.30675900
H 1.97253200 -4.27338400 -0.49405400
C 3.34313100 -2.29994100 1.74317800
H 4.02916400 -1.87561400 0.99547700
H 3.38161800 -1.67215200 2.64705000
H 3.70703700 -3.30508800 2.01111600
C 0.50286300 -3.29227200 2.33286500
H -0.53161400 -3.39719100 1.97281500
H 0.89420900 -4.30052200 2.54145800
H 0.47903000 -2.73297300 3.28101000
C 2.16018100 0.28394700 -0.71287800
C 2.36245400 0.16295200 -2.08733200
C 3.22415400 0.66145000 0.11162900
C 3.62232500 0.40975200 -2.63340400
H 1.53077300 -0.13573500 -2.72589400
C 4.47921600 0.91568400 -0.43462600
H 3.06948300 0.74983000 1.18891900
C 4.68151900 0.78732000 -1.80973000
H 3.77531600 0.30357500 -3.70928700
H 5.30384900 1.21147100 0.21704500
H 5.66686700 0.98047900 -2.23906400
Sum of electronic and zero-point Energies= -1429.079890
Sum of electronic and thermal Energies= -1429.052598
Sum of electronic and thermal Enthalpies= -1429.051654
Sum of electronic and thermal Free Energies= -1429.135104
1. Gaussian 09, Revision D.01, M. J. Frisch, G. W. Trucks, H. B. Schlegel, G. E. Scuseria, M. A.
Robb, J. R. Cheeseman, G. Scalmani, V. Barone, B. Mennucci, G. A. Petersson, H. Nakatsuji, M.
Caricato, X. Li, H. P. Hratchian, A. F. Izmaylov, J. Bloino, G. Zheng, J. L. Sonnenberg, M. Hada,
M. Ehara, K. Toyota, R. Fukuda, J. Hasegawa, M. Ishida, T. Nakajima, Y. Honda, O. Kitao, H.
Nakai, T. Vreven, J. A. Montgomery, Jr., J. E. Peralta, F. Ogliaro, M. Bearpark, J. J. Heyd, E.
Brothers, K. N. Kudin, V. N. Staroverov, T. Keith, R. Kobayashi, J. Normand, K. Raghavachari, A.
Rendell, J. C. Burant, S. S. Iyengar, J. Tomasi, M. Cossi, N. Rega, J. M. Millam, M. Klene, J. E.
Knox, J. B. Cross, V. Bakken, C. Adamo, J. Jaramillo, R. Gomperts, R. E. Stratmann, O. Yazyev,
A. J. Austin, R. Cammi, C. Pomelli, J. W. Ochterski, R. L. Martin, K. Morokuma, V. G. Zakrzewski,
G. A. Voth, P. Salvador, J. J. Dannenberg, S. Dapprich, A. D. Daniels, O. Farkas, J. B. Foresman,
J. V. Ortiz, J. Cioslowski, and D. J. Fox, Gaussian, Inc., Wallingford CT, 2013.
2. a) J.-D. Chai and M. Head-Gordon, Phys. Chem. Chem. Phys., 2008, 10, 6615–6620; b) J.-D. Chai
and M. Head-Gordon, J. Chem. Phys., 2008, 128, 084106; c) F. Weigend and R. Ahlrichs, Phys.
Chem. Chem. Phys., 2005, 7, 3297–3305.
3. a) S. Miertus, E. Scrocco and J. Tomasi, Chem. Phys., 1981, 55, 117−129; b) R. Cammi and J.
Tomasi, J. Comput. Chem., 1995, 16, 1449−1458.