82.9 Hz, aromatic), 135.2 (d, J =12.1 Hz, aromatic); 137.8
K PtCl (0.79 g, 1.9 mmol) and 3.32 g (3.8 mmol) of phosphine
P–C
2
4
(d, J =2.6 Hz, aromatic), 31P NMR (d, 100 MHz, CDCl )
4 were heated under reflux for 80 h in o-xylene (5 ml). After
removal of the solvent under vacuum, the residue was taken
again in pentane and the precipitate of KCl was filtrated.
Pentane was evaporated under vacuum and 3.3 g (1.64 mmol,
86%) of 14 was obtained as a white powder. Mp 202–204 °C;
1H NMR (d, 200 MHz, CDCl ) 1.24 (d, 3J =6.1 Hz, 108 H,
P–C
3
43.8; 29Si NMR (d, 40 MHz, CDCl ) −63.3 (d, 5J =1.5 Hz);
3
P–Si
MS (FAB+, NBA) 907 [(M+H)+, 100%]. Anal. calc. for
C H O PSi : C, 59.60, H, 8.28%. Found: C, 60.30, H, 7.96.
45 75 10
3
Methyl[tris(p-triisopropyloxysilylphenyl)]phosphonium iodide
11
3
H–H
Me), 4.28 (spt, 3J =6.1 Hz, 18 H, OCH), 7.4–7.8 (m, 24 H,
H–H
aromatic); 13C NMR (d, 50 MHz, CDCl ) 25.9 (Me), 66.0
(OCH), 130.3–137.0 (aromatic); 31P NMR (d, 100 MHz,
Phosphine 4 (4.32, 4.94 mmol) and 0.6 ml (9.63 mmol) of
methyl iodide were heated under reflux in toluene (20 ml) for
3 h. After evaporation of the solvent, 4.77 g (4.7 mmol, 95%)
of 11 were obtained. Mp 163.5–166 °C; 1H NMR (d, 200 MHz,
3
CDCl ) 13.5 [s and d (satellite 195Pt, 1J =3614 Hz), cis,
3
P–Pt
95%], 20.7 [s and d, (satellite 195Pt, 1J =2607 Hz), trans,
P–Pt
5%]; 29Si NMR (d, 40 MHz, CDCl ) −63.5 (cis), −62.7 (trans).
3
CDCl ) 1.22 (d, 3J =6.1 Hz, 54 H, Me), 3.25 (d, 2J
=
3
H–H
P–H
Anal. calc. for C H Cl O P PtSi : C, 53.63, H, 7.51, Cl,
13.0 Hz, 3 H, PMe), 4.30 (spt, 3J =6.1 Hz, 9 H, OCH),
90 150
2
18 2
6
H–H
3.47%. Found: C, 53.67, H, 7.37, Cl, 3.35.
7.60–7.96 (m, 12 H, aromatic); 13C NMR (d, 50 MHz, CDCl )
3
12.1 (d, 1J =56 Hz, PMe), 25.9 (Me), 66.5 (OCH), 120.4 (d,
P–C
trans-Bis[tris(p-triisopropyloxysilylphenyl)phosphine]
dichloroplatinum 15
J
=87.4 Hz, aromatic), 132.3 (d, J =10.2 Hz, aromatic),
P–C
P–C
136.7 (d, J =12.3 Hz, aromatic), 143.2 (s, aromatic); 31P
P–C
NMR (d, 100 MHz, CDCl ) 22.1; 29Si NMR (d, 40 MHz,
Phosphine 4 (3.46 g, 3.96 mmol) and 822 mg (1.98 mmol) of
K PtCl were refluxed for 1 h in a mixture of propan-2-ol
3
CDCl ) −65.7 (d, 5J =1.8 Hz); MS (FAB+, NBA) 889
3
P–Si
2
4
[(M−I)+, 100%]. MS (FAB−, NOBA) 127 (I−, 100%). Anal.
H, 7.97.
(25 ml) and water (15 ml). After cooling, the product was
extracted with diethyl ether which was washed with water and
dried over MgSO . After elimination of diethyl ether and
calc. for C H IO PSi : C, 54.33, H, 7.68%. Found: C, 54.58,
46 78
9
3
4
crystallisation from propan-2-ol, 1.70 g (0.844 mmol, 43%) of
pure 15 was obtained. Mp 184–191 °C; 1H NMR (d, 200 MHz,
Tris( p-triisopropyloxysilylphenyl)phosphine borane 12
A molar solution of BH ΩTHF in THF (3.5 ml, 3.5 mmol) was
CDCl ) 1.25 (d, 3J =6.1 Hz, 108 H, Me), 4.30 (spt, 3J
=
3
3
H–H
H–H
added dropwise, at 0 °C, to 2.91 g (3.33 mmol) of phosphine 4
6.1 Hz, 18 H, OCH), 7.71–7.75 (m, 24 H, aromatic); 13C NMR
(d, 50 MHz, CDCl ) 25.9 (Me), 65.9 (OCH), 130.4–136.1 (aro-
in THF (10 ml). After stirring for 1 h at room temperature,
the solvent was removed to give 2.94 g (3.31 mmol, 99%) of
12. Mp (propan-2-ol), 167–170.5 °C; 1H NMR (d, 200 MHz,
CDCl ) 1.25 (d, 3J =6.1 Hz, 57 H, Me and BH ), 4.31 (spt,
3
matic); 31P NMR (d, 100 MHz, CDCl ) 20.6 [s and d, (satellite
3
195Pt, 1J =2609 Hz)]; 29Si NMR (d, 40 MHz, CDCl ) −62.5.
Anal. calc. for C H Cl O P PtSi : C, 53.63, H, 7.51. Found:
90 150 18 2
C, 53.62, H, 7.42.
P–Pt
3
3
H–H
3
2
6
3J =6.1 Hz, 9 H, OCH), 7.50–7.80 (m, 12 H, aromatic); 13C
H–H
NMR (d, 50 MHz, CDCl ) 25.9 (Me), 66.1 (OCH), 130.9 (d,
J
3
=57.0 Hz, aromatic), 132.7 (d, J =9.2 Hz, aromatic),
Bis[tris(p-triisopropyloxysilylphenyl)phosphine]
dichloropalladium 16
P–C
P–C
135.4 (d, J =9.8 Hz, aromatic), 137.4 (d, J =2.1 Hz, aro-
matic); 31P NMR (d, 100 MHz, CDCl ) 21.1 (broad signal);
29Si NMR (d, 40 MHz, CDCl ) −63.2 (d, 5J =1.3 Hz); 11B
P–C
P–C
3
Phosphine 4 (5.86 g, 6.7 mmol) and 595 mg (3.35 mmol) of
PdCl were heated under reflux in THF (40 ml) for 3 h. The
reaction mixture was filtered and the solvent was removed
3
P–Si
NMR (d, 80 MHz, CDCl ) −37.9 (broad signal). Anal. calc.
for C H BO PSi : C, 60.79, H, 8.84%. Found: C, 60.96,
H, 8.33.
2
3
45 78
9
3
under vacuum to afford 6.4 g (3.32 mmol, 99%) of 16 as a
yellow powder. Mp (propan-2-ol) 197–198.5 °C; 1H NMR (d,
200 MHz, CDCl ) 1.24 (d, 3J =6.1 Hz, 108 H, Me), 4.30
Tris(p-triisopropyloxysilylphenyl)phosphine tungsten
pentacarbonyl 13
3
H–H
(spt, 3J =6.1 Hz, 18 H, OCH), 7.69, 7.71, 7.72 (3 s, 24 H,
H–H
aromatic); 13C NMR (d, 50 MHz, CDCl ) 25.9 (Me), 66.0
3
A THF solution of (THF)W(CO) 49 (260 ml, 14.2 mmol) was
added to 6.2 g (7.1 mmol) of phosphine 4 in THF (20 ml). The
(OCH), 134.7 (aromatic); 31P NMR (d, 100 MHz, CDCl )
5
3
23.7; 29Si NMR (d, 40 MHz, CDCl ) −62.5. Anal. calc. for
3
reaction mixture was stirred for 1 h at room temperature and
the solvent was evaporated under vacuum. After elimination
C H Cl O P PdSi : C, 56.09, H, 7.79, Cl, 3.69%. Found:
90 150
2
18 2
6
C, 55.07, H, 7.69, Cl, 3.64.
of excess of W(CO) by sublimation at 60 °C under vacuum,
8.24 g (6.88 mmol, 97%) of 13 were obtained. Mp (propan-2-
6
Tris(p-trihydrosilylphenyl)phosphine borane 17
ol), 158.5–160 °C; 1H NMR (d, 200 MHz, CDCl ) 1.25 (d,
3
3J =6.1 Hz, 54 H, Me), 4.32 (spt, 3J =6.1 Hz, 9 H, OCH),
A molar solution (5.30 ml, 5.30 mmol) BH ΩTHF in THF were
H–H
H–H
3
7.42–7.78 (m, 12 H, aromatic); 13C NMR (d, 50 MHz, CDCl )
added dropwise, at 0 °C to 1.86 g (5.28 mmol) of phosphine 4
3
25.9 (Me), 66.1 (OCH), 132.5 (d, J =11.4 Hz, aromatic),
P–C
in THF (15 ml). After 30 min at 0 °C and 1 h at room
temperature, the reaction mixture was filtered and the THF
was evaporated. The sticky product obtained was precipited
by addition of pentane (25 ml). After evaporation of pentane,
1.80 g (4.91 mmol, 93%) of 17 was obtained as a white powder.
135.3 (d, J =9.3 Hz, aromatic), 136.3 (d, J =1.7 Hz, aro-
P–C
P–C
matic), 137.0 (d, J =40.5 Hz, aromatic), 197.6 [d, 2J
=
P–C
P–C
7.0 Hz, and d of d (satellite 183W, 1J =126.0 Hz), CO (cis)],
C–W
199.7 [d, J =21.7 Hz, CO (trans)]; 31P NMR (d, 100 MHz,
P–C
CDCl ) 21.3 [s and d (satellite 183W, 1J =240.3 Hz]; 29Si
Mp 115–117 °C; 1H NMR (d, 200 MHz, CDCl ) 0.5–2 (broad
3
P–W
3
NMR (d, 40 MHz, CDCl ) −63.1 (d, 5J =1.4 Hz); IR
signal, 3 H, BH ), 4.26 [s and d (satellite 29Si, 1J =204 Hz),
3
P–Si
3
Si–H
(n/cm−1, CCl ) 1941, 1980, 2071; MS (FAB+, GT) 1198 (M+,
9 H, SiH], 7.54–7.75 (m, 12 H, aromatic); 13C NMR (d,
50 MHz, CDCl ) 130.9 (d, J =56.6 Hz, aromatic), 132.9 (d,
=9.3 Hz, aromatic), 134.4 (d, J =2.2 Hz, aromatic),
136.5 (d, J =9.8 Hz, aromatic); 31P NMR (d, 100 MHz,
CDCl ) 22.5 (broad signal); 29Si NMR (d, 40 MHz, CDCl )
−58.2 (d, 5J =1.8 Hz); 11B NMR (d, 80 MHz, CDCl ) −38.1
4
3%), 1170 [(M−CO)+, 2.4%], 1143 [(M−2CO+H)+, 5.3%],
Anal. calc. for C H O PSi W: C, 50.08, H, 6.26%. Found:
3
P–C
1114 [(M−3CO)+, 8.2%], 875 [(M−W(CO) +H)+, 18.6%].
C, 49.75, H, 6.19.
J
6
P–C
P–C
50 75 14
3
P–C
3
3
P–Si
3
cis-Bis[tris(p-triisopropyloxysilylphenyl)phosphine]
dichloroplatinum 14
(broad signal). IR (n/cm−1, CCl ) 2162; MS (FAB+, NBA)
4
365 [(M−H)+, 71%)], 352 [(M−BH )+, 87%], 245
3
Compound 14 was prepared following the procedure described
by Gillard and Pilbrow39 for the preparation of (PPh ) PtCl .
[(M−BH −C H SiH )+, 100%]. Anal. calc. for C H BPSi :
3
6
5
3
18 24
3
C, 59.01, H, 6.56%. Found: C, 58.32, H, 6.48.
3 2
2
1756
J. Mater. Chem., 1998, 8(8), 1749–1759