DETERMINACIÓN DE LA PREVALENCIA DE SÍNDROME METABÓLICO

5.1 General Experimental

All preparations were carried out under an atmosphere using standard Schlenk techniques, except where stated to the contrary. UV Photolysis was carried out using a Hanovia medium pressure UV lamp. All nmr data were obtained on a Varian VXR 400 spectrometer. Calibration of spectra was achieved by means of internal solvent resonances and externally relative to spectrometer frequency. spectra were calibrated externally relative to 85% H3PO4 / DgO at 5 0 ppm and P(0Me)3 / CDCI3 at Ô -140.4 ppm \ all ^^P nmr spectral data quoted relate to ^^P{^H} spectra. spectral data are quoted in ppm relative to Me^Si at Ô 0 ppm and referenced to the solvent.

IR spectra were obtained using a Nicolet 205 FT-IR, UV with a Shimadzu UV-160A. X-ray data were collected using an automated four-circle diffractometer (Nicolet R3mV) equipped with graphite monochromated IVIo-K^^ radiation (^=0.71073A). Column chromatography was carried out with deactivated alumina (6% w/w water). Elemental analyses were performed within the Chemistry Department of University College.

Cyclic voltammetric studies were undertaken in 0.5 M ["Bu^N][BFJ in dichloromethane at room temperature. The working electrode used was a platinum bead electrode, a platinum rod auxiliary electrode and a platinum wire quasi reference electrode were also employed. Oxidation and reduction potentials are quoted relative to [FeCp^j^^" = +0.46 V^.

Chemicals were obtained from Aldrich, Avocado or Fluorochem and used as supplied.

Solvents were distilled over the drying agents listed below, and degassed before use: dichloromethane (calcium hydride), petrols (Na/K alloy), tetrahydrofuran (potassium), toluene (Na/K alloy), chlorobenzene (P^Og).

Where the identification of a compound has been described as tentative, this is for species indicated on the basis of spectrosopic evidence but for which no sample suitable for elemental analysis was obtained.

Chapter 5: Experimental

5.2 Experimental for Chapter 1

5.2.1 Tungsten Imido Systems

[WCIJ

[W C y (21.4g, 54.0nnmol) and [W(CO)g] (9.74g, 27.7mmol) were dissolved in chlorobenzene (200ml). The solution was stirred mechanically under reflux for 16 hours. The mixture was filtered, and the resultant solids washed with purified chlorobenzene (2x50ml) and hexane (4x50ml). The product was dried under vacuum for 18 hours. [WCIJ was isolated as a grey / green powder (25.48g, 98%).

[WCIJPPh2Me)J

PPhjMe (10.3g, 51.4mmol) was added to a stirred solution of [WCIJ (7.10g, 21.8mmol) in dichloromethane (70ml) at 0°C. After 20 hours of stirring, allowing to warm to 25°C, volatiles were removed yielding a brown oil. This oil was washed with petrol (2x100ml), and a soxhlet extraction was then carried out with dichloromethane. Removal of the solvent under reduced pressure gave an orange solid (5.57g, 35% )

[WCl2(PPh2Me)J

[WCyPPhgrvIe)^] (2.52g, 3.47mmol) and PPhjMe (1.4g, 7.0mmol) were dissolved in toluene (100ml). This solution was added to Na / Hg amalgam (0.16g, 7.0mmol) and stirred for 24 hours yielding a dark green solution, which was decanted from the amalgam and filtered through 1cm Celite. The volume was reduced to half and petrol (10ml) added. Orange crystals were obtained overnight at -5°C (1.4g, 69%).

1,3-[{c/s, fra/7S-W(CO)CyPPh2Me)j2(p-NCgH,N)] (2.1)

[WCl2(PPh2Me)J (0.53g, 0.50 mmol)and 1,3-phenylene diisocyanate

(0.04g, 0.25 mmol) were stirred in toluene for 6 days to ensure complete reaction, although the mixture had gone purple after only 2 days. Solvent was removed under reduced pressure and the solid washed with 40/60 petrol to

Chapter 6: Experimental

remove residual PPhgfVle. 1,3-[{c/s, ^rans-W(C0)Cl2(PPh2lVle)2}2(n-NCgH^N)] (2.1) was obtained as dark purple crystals suitable for X-ray diffraction study (0.33g, 89%), after recrystallisation from THF.

Anal. Found: C, 47.91; H ,3.85; N, 1.84; Cl, 11.16; P, 8.55.

Calc, for: CgoHggN2CI,02P4W2'0.5CH2Cl2: C, 48.00; H, 3.77; N, 1.85; Cl, 11.73; P, 8.20%.

'H nmr (C D C y 5 7.78-7.15(m,44H, Ph), 2.27 (t, J 3.9 Hz, 12H, Me) "'P nmr (C D C y 5 2.14 (s, Jp^ 290 Hz)

IR (v(C O )) (CH^Cy 1966

UVA/is (C H jC y (A.,^(nm),e (dm^mor^cm"')) 844, e 75; 308, e 1390; 234, e 4220 Epc(irrev)-1.36 V

1,4-[{c/s, fra/7S-W(CO)Cl2(PPh2Me)2}2(p-NCgH^N)] (2.2)

[WCyPPhjMe)^] (1.80g,1.70 mmol) and 1,4-phenylene diisocyanate (0.14g, 0.85 mmol) were stirred in toluene. Recrystallisation from chlorobenzene / MeOH yielded 1,4-[{W(C0)Cl2(PPh2Me)2}2(p-NCgH^N)] (2.2) as dark green crystals (1.17g, 93%). 'H nmr

(CDCy 5 7.37-7.09

3.9

(CDCy

UVA/is (CHgCy (A.,^(nm),e (dm^mol 'cm ')) 382, s 4175; 235, e 9 9 3 5

^pc(irrev) -1.08 V ^pa(irrev) +1.05 V

1,3-[{W(C0)Cl2(PPh2Me)2}2(p-N-4-(IVIe)CgH,N)] (2.3)

[WCyPPhgMe)^ (0.20g,0.19mmol) and 1,3-toluylene diisocyanate (1,3-{OCN-4-(Me)-CgH3NCO}) (0.017g, 0.09 mmol) were stirred in toluene. After 2 hours the reaction mixture was claret red, and after 4 hours a new IR band

Chapter 5: Experimental

total, after which volatiles were removed under reduced pressure. The residue was washed with petrols and remaining volatiles removed under vacuum. Mauve rhombohedral crystals were obtained from CH^CIg / MeOH (0.13g, 92%).

Anal. Found: 0, 47.98; H , 3.81; N. 1.76 ; Cl. 11.67 ; P, 8.44.

Calc, for: CG.HsgNgCI.OzP.Wg'O.SCHzClz: C, 48.37; H, 3.89; N, 1.83; Cl, 11.61; P, 8.11%. "'P nmr (C D C y Ô 3.3 (s, 291 Hz). 2.20 (s,Jp^ 291 Hz) IR: (v(CC)) (CHgCy (cm"") 1966 IR (KBr) (cm-') 1996 (s. (v(CC)), 1961 (s. (v(CC)). 1481 (m), 1432 (m), 1340 (w), 1315 (w), 1271 (w), 1095 (m, v(W fN)), 895 (s), 891 (s), 734 (m). 730 (m), 693 (s), 498 (m), 488 (w), 450 Cm) \ UVA/is (C H jC y (W n m ),G (dm^mol 'cm ')) 1053, s 15; 813, e 15; 555, e 50; 311, G 3360; 236, g 10325 Hpc(irrev) -1.21 V

Reaction of [W CyPPhM e^jJ and OCN-fCHJg-NCO

[WC^PPhMeg)^ (0.33g, 0.31 mmol) and CCN-(CH2)g-NCC (0.03g,

0.15mmol) were stirred in toluene overnight. The mixture had gone red after 1 hour. Volatiles were removed under reduced pressure, and the residue washed with petrols (2 x 40 ml). Left under reduced pressure for 12 hours it was found that the reddish mauve residue remained oily. Recrystallisations from the following were unsuccessful: chlorobenzene, chlorobenzene / petrol, CH^CIg / MeCH, CHgClg / petrol, toluene, toluene / petrol. The product has been tentatively identified as [{W(CC)Cl2(PPh2Me)2}2(N (C H j6N)]

"'P nmr (C D C y Ô 3.2 (s, = 295.4Hz) IR: (v(CC)) (CH^Cy (cm"') 1962

Reaction of [WCI^CPPhMeJJ and OCN-CgH^-ICHJ-CgH^-NCO

[WCyPPhMe^),] (0.33g, 0.31 mmol) and CCN-CgHXCHJ-CGH.-NCC (0.04g, 0.15mmol) were stirred in toluene (50ml) for 3 days. The mixture was dark green / brown, the IR spectrum showed a band at 1963 cm"'. However, the expected colour change (to a red or mauve colour) had not occurred.

Chapter S: Experimental

OCN-CgHXCHJ-CgH^-NCO (0.04g, 0.15mmol) was added, and stirred over a period of 3 days, after which nmr revealed that a paramagnetic species was present. This was assumed to be [WCyPPhlVIeg)^; volatiles were removed under reduced pressure, the mixture washed with petrols ( 2 x 50ml) and

thoroughly dried under vacuum before being dissolved in THF (50ml).

0 CN-CgHXCH2)-CgH^-NC0 (0.1g, 0.40mmol) was added and the mixture stirred

overnight. Removal of volatiles under reduced pressure, followed by washing with petrols (3 x 50ml) and 12 hours further removal of volatiles under reduced pressure yielded a dark brown oily residue. Recrystallisation from the following was unsuccessful: chlorobenzene, chlorobenzene / petrol, CH^CIg / MeOH, CH^CIg / petrol, toluene, toluene / petrol. The product has been tentatively identified as [{W(C0 )Cl2(PPh2M e )j2-(N-CgHXCH2)-CgH,-N)]

^'P nmr (C D C y ô 2.95 (s, 283.2Hz) IR: (v(CO)) (C H jC y (cm ') 1963

5.2.2 Molybdenum Dithiocarbamate Systems [M o(0),(S2CNEt,)J (2.4)^

NaS2CN(Et)2.3 H2 0 (16.0g, Tl.Ommol) and NaMo0 ^.2 H2 0 (14.5g,

60.0mmol) were dissolved in water (300ml). HCI (315ml, 0.6M) was added over 45 minutes, with stirring, precipitating a brown solid. This precipitate was washed with water (2x100ml). The solid was purified by recrystallization from benzene and petroleum spirit (14.6g, 97%)

[Mo(0)S2(S2CNEy2]“

[Mo(0 )2(S2CNEt2)2] (2.4) (2.22g, 5.23 mmol) was dissolved in CH2CI2 (50

ml). PPhj (1.37g, 5.23 mmol) was added with stirring. The resultant solution was then refluxed for 3 hours yielding a red solution of [MoO(S2CNEt2)2] (2.4). On

cooling, propylene sulphide (1.27g, 17mmol) was added and the solution stirred for a further hour to give a blue/green solution. Volatiles were removed under reduced pressure to yield a blue solid [Mo(0 )S2(S2CNEt2)2] (2.8) (2.07g, 90%),

Chapter S: Experimental

[IVIo(O yS,CNM eJJ (2.5)®°

N a$2CN(Me)2.3 H2 0 (35.8g, 20.0mmol) and NalVloO,.2 H2 0 (14.5g,

GO.Ommol) were dissolved in water (300ml). HCI (315ml, 0.6M) was added over 45 minutes, with stirring, precipitating a brown solid. This precipitate was washed with water (2x100ml). The solid was purified by recrystallization from benzene and petroleum spirit (14.6g, 97%)

Reaction of [M o(0 )2(S2CNEt2)J (2.4) and 1,4-{0CN-(CgHJ-NC0}

[Mo(0 )2(S2CNEt2)2] (2.4) (5.30g, 12.5 mmol) and 1,4-{0CN-(C6HJ-NC0}

(I.Og, 6.25 mmol) were dissolved in toluene and refluxed for 3 days, after which the mixture was found to be a green solution with brown solids. Volatiles were removed and the resultant solid adsorbed onto alumina, column chromatography was then carried out, the results of which are set out in the table below:

Band Colour Yield

1. 60-80% CH2Cl2/petrol Yellow 0.83g, 13%

2. 80-90% CH2Cl2/petrol Dark green 1.62g, 26%

3. 90-100% CH2Cl2/petrol Purple / red 1.90g

4. 100% CH2CI2 Orange 0.63g

5. 10-20% M e O H /C H2CI2 Red 0.40g

Further data are given below: Where fully characterised, recrystallisation was from CH2CI2 / MeOH; where partially characterised recrystallisation was

unsuccessful from: CH2CI2 / MeOH, CH2CI2 / petrol, toluene, toluene /petrol, THF,

THF / petrol.

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