6.4. Systems using Paraformaldehyde as a Substrate
6.6.4. Product Analysis
a) Gas Chromatography - Mass Spectroscopy, GCMS
Qualitative analysis of products from catalytic experiments was carried out by GCMS on an INCOS 50 GCMS system with a Hewlett Packard 5890 gas chromatograph. The gas chromatograph was run with a silica capillary column using a methyl siloxane stationary phase. Helium at 9 psi was used as carrier gas and the injector temperature was 200°C. The g.c. temperature program was set to run at 40°C for 5 minutes and was then raised, at 10° per minute, to 200°C, where it was held for 10 minutes. All samples were run undiluted, as reaction mixtures, on removal from the autoclave.
b) Gas Liquid Chromatography, glc
Products of catalytic runs were analysed quantatively by glc
on a Phillips PU 4500 chromatograph using nitrogen as the carrier gas, with the injector tem perature set at 200<^C, and a flame ionisation detector at 250°C. Reaction solutions were diluted by a factor of 10 with ethanol prior to injection of 1 pi. Calculations were carried out assuming
A ppendix One
General Experimental Techniques
A l.l. Equipment and Reagents Al.1.1. Vacuum Lines
The work with air-sensitive reagents in this thesis was carried out on a standard Schlenk Line (with greaseless taps and ball and socket compression joints), using syringe and catheter tubing techniques. An inert atmosphere was provided by either nitrogen or argon (white spot
grade), which was dried by passage through a column packed with chromium (II) adsorbed onto silica.
A l.l.2. Solvents
Alcoholic solvents (methanol and ethanol) were dried prior to use by distillation over magnesium, under an atmosphere of nitrogen. Petrol (40-600 boiling range), diethyl ether, and THF were dried by distillation from sodium benzophenone under a nitrogen atmosphere. Toluene was dried by distillation over sodium under a nitrogen atmosphere. CH2CI2
was distilled over calcium carbonate under a nitrogen atmosphere prior to use. Nitromethane was stored over activated molecular sieves (4 Â) and de-gassed thoroughly with nitrogen or argon before use.
A l.l.3. Reagents
The following chemicals were used as supplied, w ithout further purification: PdCl2, K2PtCl^, Na2PdCl4 (Johnson Matthey), RhClg.H2 0
(Johnson Matthey or Aldrich), CH2I2/ CH2Br2, AgSbF^, PMeg, dppp,
PCy3 (Strem), and ICH2C(0 )C1 (Lancaster). All were degassed thoroughly
prior to use, unless supplied under nitrogen. A1.2. Product Analysis
Al.2.1. Nuclear Magnetic Resonance Spectroscopy, nmr
All nmr spectra were recorded on a Brucker AM300 Spectrometer (:H 300.1MHz., 31p 121.5 MHz., 13C 75.5 MHz.) in 5mm glass tubes, ^H, 3lp, and 13c spectra of compounds were recorded in solutions of THF-dg, CgDg, CD3OD, CD2CI2, or CD3NO2. For iH spectra, the solvent shifts
were used as internal references, whilst 31 p spectra were run relative to external H3PO4, with shifts to high frequency quoted positive.
Al.2.2 Infra-red Spectroscopy, IR
All infra-red spectra were recorded on a Perkin-Elmer 1710 Infrared Fourier Transform Spectrometer in the range 4000-400 cm'l. Spectra were recorded either as nujol mulls between Csl discs, or as solutions in a KBr cell.
Al.2.3. Elemental Analysis
C, H microanalysis was carried out by the University of St. A ndrew s Microanalytical Service, using a Carlo Erba MOD 1106 elemental analyser.
Appendix Two
Determination of the Crystal Structure of trans- RhCl(CO)(CH2l)I{PEt3)2
Experimental
Orange crystals of RhCl(CO)(CH2l)I(PEt3 )2 were obtained by
recrystallisation of the complex from ether/petrol. The solution was kept at room temperature (and in the dark) during dissolution an filtration, then cooled to -20°C for 48 hours to obtain crystals. These were filtered whilst cold, then washed with petrol at -78°C (cardice/ethanol bath), and dried in vacuo. They were stable indefinitely under N2, and it was
possible to handle them briefly in air without apparent decomposition. A crystal measuring 0.92 x 0.2 x 0.32mm was sealed in a Lindemann
glass capillary. Cell dimensions were refined from 25 carefully centred reflections (8°<b<13°) using an Enfaf-Nonius CAD4 diffractometer (SERC service at QM\V, London). 8 6 6 6 measured reflections yielded 7897
unique data, of which 6547 were used in the refinement.
Data were collected in the range 1.5°<i}<2.5° for index limits 0<h<14, -17<k<17, -18<1<18, and corrected for absorbtion by a T scan on the diffractometer.
Crystallographic Data
Formula: C|4H32C10l2P2Rh/ Mw = 670.5155, triclinic. P, a = 12.343(3)A, b = 14.327(2)Â, c = 15.426(2)Â, a = 113.78(1)o, p = 67.25(1)°, 7 =
90.20(1)0, v = 2264.23Â3, Z = 4, = 1.967Mgm-3, X(MoKa) = 0.7106Â, |x = 8.37cm-l, F(OOO) = 897.95, T = 293K.
The structure was solved by the use of direct methods, employing the SHELXS8 6 program^^l. From early E-MAPS, it was obvious that two
distinct structures were present, so this was incorporated into later refinements, using least squares and difference Fourier map techniques. Atomic geometry calculations used XANADU^^^2^ and drawings were prepared with PLUT0^23^
Final Refinement
(Minimising Eco(Fq-[Fj,])2 217 refined parameters. R = 0.0453, coR =
0.0529, CO = 2.1508/(a2(F) + 0.000497F2), mean shift/e.s.d. = 0.0005, max.
shift/e.s.d. = +0.0104. Max. peaks on final difference map = 0.302, -0.119eÂ-3.
Table A2.1 I n t e r a t o m i c d i s t a n c e s (A) a n d a n g l e s ( ° ) C L 2 --- R Hl 2 . 3 7 4 ( 2 ) 1 3 ———RHl 2 . 8 0 3 1) C4 --- R H l 1 . 8 2 7 ( 9 ) 0 6 ———RHl 2 . 0 6 3 9) P 8 --- R Hl 2 . 3 8 6 ( 3 ) P I S --- RHl 2 . 3 9 3 3 ) 0 5 ———C4 1 . 1 4 0 ( 1 1 ) I 7 --- 0 6 2 . 1 2 1 1 0 ) C 9 --- P 8 1 . 8 3 4 ( 1 0 ) 0 1 1 --- P8 1 . 8 2 4 8) C 1 3 --- P8 1 . 8 2 7 ( 8 ) O l O --- 0 9 1 . 5 0 2 1 8 ) C 1 2 ---C i l 1 . S 0 8 ( 1 4 ) 0 1 4 —— 0 1 3 1 . 4 9 3 1 2 ) 0 1 6 --- P I S 1 . 8 2 9 ( 6 ) 0 1 8 --- P I S 1 . 8 2 9 1 0 ) 0 2 0 --- P I S 1 . 8 4 9 ( 1 2 ) 0 1 7 --- 0 1 6 1 . 5 3 5 1 4 ) 0 1 9 --- 0 1 8 1 . 4 9 4 ( 1 6 ) 0 2 1 --- 0 2 0 1 . 4 9 4 1 7 ) O L 3 2 ---RH31 2 . 3 8 1 ( 3 ) I 3 3 — RH31 2 . 7 6 5 1) 0 3 4 --- RH31 1 . 8 4 9 ( 1 1 ) 0 3 6 --- RH31 2 . 0 8 0 6) P 3 8 --- RH31 2 . 3 7 8 ( 2 ) P 4 5 --- RH31 2 . 3 9 8 2) 0 3 S ---0 3 4 1 . 0 9 9 ( 1 4 ) 1 3 7 --- 0 3 6 2 , 1 5 1 9) 0 3 9 ---P 3 8 1 . 8 4 2 ( 8 ) 0 4 1 — —P 3 8 1 . 8 2 8 1 4 ) 0 4 3 --- P 3 8 1 . 8 1 7 ( 8 ) 0 4 0 --- 0 3 9 1 . 4 9 8 2 0 ) 0 4 2 --- 0 4 1 1 . 5 4 6 ( 1 5 ) 0 4 4 --- 0 4 3 1 . 5 2 8 1 4 ) 0 4 6 --- P 4 S 1 . 8 2 7 ( 1 2 ) 0 4 8 — P 4 S 1 . 7 9 5 7) o s e --- P 4 S 1 . 8 1 S ( 1 2 ) 0 4 7 --- 0 4 6 1 . 4 6 4 2 2 ) 0 4 9 --- 0 4 8 1 . 5 6 7 ( 1 6 ) o s i — 0 5 0 1 . 5 2 6 1 4 ) 1 3 - R H l - 0 L 2 9 8 . 3 1) 0 4 - R H l - 0 L 2 1 7 9 . 4 3) 0 4 - R H l - 1 3 8 2 . 2 3) 0 6 - R H l - C L 2 8 4 . 5 2) 0 6 - R H l - 1 3 1 7 6 . 7 2) 0 6 - R H l - 0 4 9 5 . 0 4) P 8 - R H l - 0 L 2 8 7 . 4 1) ? 8 - R H l - 1 3 8 7 . 7 1) P 8 - R H l - 0 4 9 2 . 9 3 ) P 8 - R H l - 0 6 9 0 . 7 3) P I S - R H l - 0 L 2 8 7 . 3 1 ) P I S - R H l - 1 3 9 1 . 4 1) P I S - R H l - 0 4 9 2 . S 3) P I S - R H l - 0 6 9 0 . 5 3) P I S - R H l - P 8 1 7 4 . 4 1) 0 5 - 0 4 - R H l 1 7 7 . 8 7) 1 7 - 0 6 - R H l 1 2 0 . 3 4) 0 9 - P 8 - R H l 1 1 2 . 4 3) 0 1 1 - P 8 - R H l 1 1 7 . S 4) 0 1 1 - P S - 0 9 1 0 3 . 9 5) 0 1 3 - P S - R H l 1 1 3 . 8 4) 0 1 3 - P S - 0 9 1 0 5 . 7 5) 0 1 3 - P S - 0 1 1 1 0 2 . 2 4) OlO - 0 9 - P S 1 1 7 . 2 5) 0 1 2 - 0 1 1 - P S 1 1 4 . 7 S) 0 1 4 - 0 1 3 - P 8 1 1 6 . 8 7) 0 1 6 - P I S - R H l 1 1 7 . S 4) 0 1 8 - P I S - R H l 1 1 2 . 2 3) 0 1 8 - P I S - 0 1 6 1 0 5 . 2 4) 0 2 0 - P I S - R H l 1 1 5 . 5 3) 0 2 0 - P I S - 0 1 6 1 0 2 . 3 4) 0 2 0 - P I S - 0 1 8 1 0 2 . 5 5 ) 0 1 7 - 0 1 6 - P I S 1 1 6 . 1 6) 0 1 9 - 0 1 8 - P I S 1 1 8 . 4 7 ) 0 2 1 - 0 2 0 - P I S 1 1 3 . 3 1 0 ) 1 3 3 - R H 3 1 - O L 3 2 9 2 . 9 0 ) 0 3 4 - R H 3 1 - O L 3 2 - 1 7 8 . 6 2) 0 3 4 - R H 3 1 - 1 3 3 8 8 . 5 2) 0 3 6 - R H 3 1 - O L 3 2 8 4 . S 3 ) 0 3 6 - R H 3 1 - 1 3 3 1 7 7 . 2 3) 0 3 6 - R H 3 1 - 0 3 4 9 4 . 1 3 ) P 3 8 - R H 3 1 - O L 3 2 8 8 . 1 1 ) P 3 8 - R H 3 1 - I 3 3 9 1 . 0 0) P 3 8 - R H 3 1 - 0 3 4 9 2 . 0 3) P 3 8 - R H 3 1 - 0 3 6 9 0 . 1 2 ) P 4 S - R H 3 1 - C L 3 2 9 0 . 5 1 ) P 4 5 - R H 3 1 - I 3 3 8 5 . 3 0) P 4 S - R H 3 1 - 0 3 4 8 9 . 5 3) P 4 S - R H 3 1 - 0 3 6 9 3 . 6 2 ) P 4 S - R H 3 1 - P 3 8 1 7 6 . 0 1) 0 3 S - 0 3 4 - R H 3 1 1 7 9 . 6 S) 1 3 7 - 0 3 6 - R H 3 1 1 1 9 . 9 5 ) 0 3 9 - P 3 8 - R H 3 1 1 1 7 . 5 3) 0 4 1 - P 3 8 - R H 3 1 1 1 3 . 1 4) 0 4 1 - P 3 8 - 0 3 9 1 0 0 . 6 5 ) 0 4 3 - P 3 8 - R H 3 1 1 1 3 . 8 3) 0 4 3 - P 3 8 - 0 3 9 1 0 3 . 2 5) 0 4 3 - P 3 8 - 0 4 1 1 0 7 . 2 4) 0 4 0 - 0 3 9 - P 3 8 1 1 7 . 5 7 ) 0 4 2 - 0 4 1 - P 3 8 1 1 5 . 6 8) 0 4 4 - 0 4 3 - P 3 8 1 1 5 . 2 6) 0 4 6 - P 4 S - R H 3 1 1 1 3 . 2 4) 0 4 8 - P 4 S - R H 3 1 1 1 8 . 0 3) 0 4 8 - P 4 5 - 0 4 6 1 0 4 . 4 5) OSO - P 4 5 - R H 3 1 1 1 2 . 0 3) 0 5 0 - P 4 S - 0 4 6 1 0 4 . 8 5 ) OSO - P 4 5 - 0 4 8 1 0 3 . 0 S) 0 4 7 - 0 4 6 - P 4 S 1 1 5 . 7 7 ) 0 4 9 - 0 4 8 - P 4 S 1 1 3 . 8 7) 0 5 1 - 0 5 0 - P 4 S 1 1 7 . 6 8)
Table A2.2 C o o r d i n a t e s x 1 0 ^ f o r h y d r o g e n a t o m s x / a y / b z / c H 6 1 - 1 1 4 9 1 7 1 4 3 5 8 2 H62 - 2 9 9 5 5 2 3 2 8 7 H 9 1 - 2 4 6 1 3 6 3 5 4 4 H92 7 1 6 2 2 5 6 4 0 3 H l O l - 8 3 6 2 4 2 2 - 1 3 2 H 1 0 2 - 9 7 3 3 5 5 4 9 7 2 H 1 0 3 - 1 9 3 5 2 6 6 0 1 1 1 4 H i l l - 2 4 2 0 3 2 7 4 2 9 2 1 H 1 1 2 - 2 0 8 7 2 8 2 8 3 7 1 7 H 1 2 1 - 3 3 3 9 1 7 8 8 2 9 7 9 H 1 2 2 - 1 9 2 6 1 0 4 5 2 5 0 4 H 1 2 3 - 2 2 5 9 1 4 9 1 1 7 0 8 H 1 3 1 - 6 4 3 4 3 0 6 2 3 6 5 H 1 3 2 7 4 0 3 9 8 3 2 3 5 6 H 1 4 1 - 5 6 8 5 3 6 7 3 9 9 9 H 1 4 2 - 2 7 2 4 2 5 1 4 1 5 0 H 1 4 3 - 1 6 5 5 . 4 5 7 4 4 1 5 8 H 1 6 1 4 2 6 6 - 8 7 4 1 1 6 4 H 1 6 2 4 1 9 5 1 3 1 7 9 4 H 1 7 1 4 2 6 9 - 1 5 4 4 - 5 6 6 H 1 7 2 2 8 9 8 - 7 1 6 — 4 3 H 1 7 3 2 9 6 8 - 1 7 2 2 3 2 7 H 1 8 1 1 1 5 7 - 9 5 0 2 2 2 5 H 1 8 2 1 1 2 0 - 2 6 1 3 4 7 9 H 1 9 1 1 9 1 3 - 2 0 6 5 2 7 5 4 H 1 9 2 3 0 0 6 - 1 3 0 3 2 9 1 8 H 1 9 3 3 0 4 3 - 1 9 9 1 1 6 6 4 H 2 0 1 3 4 8 9 2 6 7 3 2 7 1 H 2 0 2 2 4 2 7 1 4 2 0 3 9 3 2 H 2 1 1 4 4 4 3 1 7 6 5 3 4 0 2 H 2 1 2 3 7 1 2 2 0 8 3 2 7 5 0 H 2 1 3 4 7 7 4 9 3 0 2 0 8 9 H 3 6 1 2 7 1 7 5 2 9 1 8 7 6 5 H 3 6 2 1 6 8 3 4 5 4 4 8 4 2 2 H 3 9 1 7 0 2 3 2 8 4 8 6 5 0 H 3 9 2 4 5 4 2 0 6 6 7 9 0 4 H 4 0 1 - 5 4 1 3 4 5 0 7 8 2 7 H 4 0 2 5 8 4 2 6 2 7 6 5 8 9 H 4 0 3 8 3 2 3 8 4 4 7 3 3 5 H 4 1 1 1 8 7 1 9 6 9 7 9 1 4 H 4 1 2 2 5 0 5 1 8 9 4 8 6 4 5 H 4 2 1 3 7 2 4 1 5 6 7 7 6 1 H 4 2 2 4 5 2 1 9 9 1 7 2 7 3 H 4 2 3 3 8 8 7 6 6 6 5 4 1 H 4 3 1 3 6 7 8 9 0 1 5 4 9 8 H 4 3 2 2 6 8 6 1 8 0 1 5 5 1 8 H 4 4 1 2 1 5 4 8 1 4 9 7 9 H 4 4 2 1 0 2 2 9 7 1 6 1 7 7 H 4 4 3 2 0 1 4 7 1 6 1 5 7 H 4 6 1 5 6 2 8 4 1 6 1 5 5 4 6 H 4 6 2 6 7 2 7 4 7 9 2 5 8 9 5 H 4 7 1 5 6 2 5 5 8 0 1 5 5 0 0 H 4 7 2 5 3 8 0 6 4 1 6 6 8 2 4 H 4 7 3 4 2 8 2 5 7 8 5 6 4 7 5 H 4 8 1 3 9 1 2 6 2 1 8 8 4 3 6 H 4 8 2 5 4 1 4 6 3 3 8 8 1 8 5 H 4 9 1 4 2 3 6 6 7 1 3 1 0 0 4 4 H 4 9 2 5 3 4 2 5 5 9 4 9 4 0 9 H 4 9 3 3 8 4 1 5 4 7 4 9 6 6 1 180
Table A2.3 A n i s o t r o p i c t e m p e r a t u r e f a c t o r s X 1 0 ' w i t h e . s . d ' s i n p a r e n t h e s e s Ü 1 1 0 2 2 0 3 3 0 2 3 0 1 3 0 1 2 1: RHl 3 4 1) 3 3 1) 3 3 1) 1 3 1) - 1 3 1 ) - 5 1) CL2 68 1) 38 1) 6 1 1) 1 1 1) - 3 9 1) - 8 1 ) 1 3 4 8 1) 7 5 1) 62 1) 4 1 1) - 1 1 1) - 5 1 ) C4 5 5 5) 4 5 4) 6 3 5) 2 2 4) -28 4) - 8 4) 0 5 9 7 5) 5 6 4 ) 86 5) 1 8 3 ) - 6 7 4 ) - 2 7 3) C6 4 8 5) 6 1 5) 6 1 5) 3 6 4) -16 4 ) - 6 4 ) A 1 7 7 7 1) 1 4 2 1) 4 5 1) 3 5 1 ) - 1 5 1 ) -13 1 ) A P 8 3 8 1 ) 3 6 1) 4 3 1) 1 5 1) -18 1 ) - 5 1 ) C9 7 1 6) 5 2 4) 4 9 5) 1 7 4) - 3 5 4) 0 4) 1 CIO 7 9 6) 7 2 6) 88 7) 4 7 5) - 5 1 6) - 1 1 5 ) t C l l 3 7 4) 6 0 5 ) 7 8 6) 3 6 5) -20 4 ) —1 6 4) C 1 2 5 7 6) 1 0 1 8) 1 0 6 8) 5 6 7 ) - 4 1 6) - 2 5 6) * C 1 3 67 5 ) 33 4) 6 4 5) 1 3 4 ) - 3 3 4) — 6 4) ? C 1 4 8 6 7) 52 5) 7 0 6) 7 5) - 4 1 6) 6 5 ) : P 1 5 3 9 1) 4 5 1) 4 5 1) 2 1 1) - 1 6 1 ) - 2 1) ’Î C 1 6 3 4 4) 68 5) 5 6 5) 2 7 4) - 6 4) 3 4) C 1 7 7 5 7) 68 6) 52 5) 1 7 5) - 9 5 ) 9 5 ) C 1 8 4 8 5) 5 4 5) 7 9 6) 3 9 5) - 2 1 4) —1 4) C 1 9 85 7 ) 7 0 6) 1 0 9 9) 5 7 6) - 2 9 7 ) 4 6) C 2 0 5 7 5) 7 3 6) 7 7 6) 3 1 5) - 4 0 5 ) - 6 5 ) C 2 1 8 7 8) 1 0 2 9) 1 1 9 1 0 ) 4 1 8) — 6 4 8) - 3 4 7) RH 31 4 0 1) 3 1 1 ) 2 9 1) 1 0 1 ) - 1 5 1) - 1 1 ) - C L 3 2 7 2 1) 7 5 1 ) 6 7 1) 4 7 1) - 4 1 1) -22 1) 1 3 3 5 3 1) 5 9 1) 5 5 1) - 6 1 ) - 7 1 ) - 5 1) C 3 4 4 4 4) 4 1 4) 5 2 4) 1 5 3) -23 4) 3 3) 0 3 5 7 5 4) 8 1 4) 7 1 4) 3 9 4) - 4 7 4) - 8 3) 1 C 3 6 5 0 5) 46 4) 4 6 4) 1 6 3) - 1 6 4) 4 3) i ; 1 3 7 82 1 ) 9 0 1) 3 5 1) 1 4 1) - 8 1) — 4 1) 1 ... 1 P 3 8 4 6 1) 42 1) 4 2 1) 1 9 1) - 2 0 1) —1 0 1) C 3 9 4 5 5) 7 0 5 ) 5 1 5) 1 8 4 ) - 1 6 4) - 1 3 4 ) C 4 0 65 6) 85 7) 9 0 8) 3 6) - 4 8 6) 9 5 ) C 4 1 8 2 7) 68 6) 8 5 7) 5 1 5) - 4 3 6) —3 0 5 ) C 4 2 1 3 0 1 0 ) 4 7 5) 1 2 7 1 0 ) 3 2 6) - 7 9 9) - 1 7 6) C 4 3 7 2 6) 4 8 4) 4 3 4) 1 0 4) - 2 4 4) - 2 3 4 ) i i C 4 4 8 0 6) 4 2 4) 7 1 6) 1 4 4) - 4 0 5) - 1 7 4) : 5 P 4 5 5 1 1) 3 9 1) 4 2 1) 1 7 1) - 2 3 1) - 1 0 1 ) C 4 6 7 3 6) 1 1 3 8 ) 5 9 5) 5 9 6) - 3 3 5) - 4 4 6) ' i 'Î C 4 7 2 2 6 1 8 ) 1 1 3 1 0 ) 1 1 4 1 1 ) 8 5 9) -87 1 2 ) - 7 0 1 2 ) ! C 4 8 7 3 6) 4 0 4) 6 1 5) 1 3 4 ) - 3 3 5) - 6 4) 1 C 4 9 1 2 1 9) 65 6) 5 1 5) 1 1 5) - 3 9 6) - 1 8 6) C 5 0 6 1 5) 4 9 5) 7 9 6) 2 2 4) - 4 1 5) - 1 6 4 ) C 5 1 5 3 5) 6 9 6) 1 1 2 8) 3 1 6) - 4 5 6) - 2 7 5) 181
Table A2.4 C o o r d i n a t e s X 1 0 ^ f o r n o n h y d r o g e n a t o m s w i t h e . s . d ' s i n p a r e n t h e s e s . U e q X 1 0 ^ . = (l/3)ZiZjUija*a;ai.aj x / a y / b z / c U e q R Hl 1 0 3 7 1) 1 5 2 1 1) 2 3 0 3 1) 3 4 1 CL2 4 9 3 2) 6 5 1) 1 2 2 2 2) 5 5 1 1 3 2 8 5 8 1) 1 8 4 6 1) 7 2 7 1) 6 2 1 C4 1 4 4 9 7) 2 6 3 9 6) 3 1 4 5 7) 5 3 2 0 5 1 7 4 3 6) 3 3 2 6 5) 3 6 4 5 5) 7 5 2 C6 - 3 2 4 7) 1 3 7 3 7) 3 5 1 5 6) 5 6 2 1 7 - 3 7 2 1) 2 0 3 4 1) 5 0 3 5 1) 9 4 1 P8 - 3 4 1 2) 2 5 8 4 1) 2 1 9 3 1) 4 0 1 C9 - 1 6 9 8) 2 1 7 1 6) 8 4 9 6) 5 6 2 CIO - 1 0 3 9 9) 2 7 4 2 7) 6 9 0 8) 7 0 3 C l l - 1 9 2 9 7 ) 2 6 5 4 6) 2 9 2 4 7) 5 8 2 C 1 2 - 2 3 9 7 9) 1 6 7 5 8) 2 4 9 9 9) 8 2 4 C 1 3 - 2 0 0 8) 3 9 5 0 5 ) 2 6 6 7 7) 5 6 2 C 1 4 - 7 0 9 9) 4 5 7 9 7) 3 8 2 4 7) 7 4 3 P 1 5 2 4 1 4 2) 3 2 0 1) 2 2 6 7 1) 4 3 1 C 1 6 3 7 1 0 7) - 4 1 7 7) 1 0 2 9 6) 5 8 2 C 1 7 3 4 4 1 9) - 1 1 5 4 7) 1 1 9 7) 7 5 3 C 1 8 1 6 9 4 7) - 6 5 4 6) 2 6 5 3 7) 5 9 2 C 1 9 2 4 6 8 1 0 ) - 1 5 6 6 8) 2 4 8 6 9) 8 6 4 C 2 0 3 1 1 1 8) 8 8 6 7) 3 1 8 5 8) 6 6 3 C 2 1 4 0 7 7 1 0 ) 1 4 5 5 1 0 ) 2 8 3 2 1 1 ) 9 9 5 RH31 3 8 2 4 1) 3 4 2 9 1) 7 3 3 8 1) 3 5 1 C L 3 2 3 1 2 7 2) 3 9 9 9 2) 6 3 6 3 2) 6 1 1 1 3 3 5 6 8 5 1) 1 9 8 6 1) 5 5 6 4 1) 7 2 1 C 3 4 4 3 3 8 7) 3 0 1 1 5 ) 8 1 2 5 6) 4 7 2 0 3 5 4 6 4 4 6) 2 7 5 7 5 ) 8 5 8 9 5) 6 8 2 C 3 6 2 4 2 4 7) 4 5 5 4 6) 8 6 3 2 6) 5 1 2 1 3 7 1 7 4 7 1) 4 4 6 4 1) 1 0 1 0 2 1) 8 0 1 P 3 8 2 5 2 4 2) 2 2 0 0 1) 7 2 2 6 1) 4 3 1 C 3 9 9 0 7 7) 2 7 0 5 7) 7 8 6 8 7) 6 0 2 C 4 0 4 1 1 9) 3 1 9 1 8) 7 3 7 0 9) 8 7 4 C 4 1 2 6 0 5 9) 1 3 8 9 7) 7 8 6 7 8) 6 9 3 C 4 2 3 7 7 2 1 1 ) 5 9 0 7) 7 3 1 9 1 0 ) 9 5 5 C 4 3 2 7 7 7 8) 1 3 3 4 6) 5 8 9 6 6) 5 8 2 C 4 4 1 9 3 0 9) 5 5 7 5) 5 7 9 5 7) 6 6 3 P 4 5 5 2 2 0 2) 4 5 9 7 1) 7 3 2 3 1) 4 4 1 C 4 6 5 7 7 9 9) 4 7 9 9 8 ) 6 1 4 0 7) 7 2 3 C 4 7 5 2 3 0 1 6 ) 5 7 6 3 1 0 ) 6 2 4 2 1 1 ) 1 3 3 7 C 4 8 4 7 3 8 8) 5 8 8 3 6) 8 3 7 2 7) 5 9 2 C 4 9 4 5 2 2 1 1 ) 5 9 1 9 8) 9 4 5 6 7) 8 3 4 C 5 0 6 5 4 5 8) 4 1 1 6 6) 7 3 6 9 8) 6 2 3 C 5 1 7 5 3 0 8) 4 7 6 6 7) 7 3 2 4 9) 7 8 3
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