Group 13 Phosphinimine and Phosphinimide Complexes
Organometallics, Vol. 18, No. 20, 1999 4199
m), 7.0 (12H, m), 2.7 (1H, br t), 0.3 (18H, s). 13C{1H} NMR
-90.6 (t, |J B-F| ) 20.3 Hz). (28) 1H NMR (CD2Cl2): δ 1.9 (12H,
m), 1.8 (3H, m), 1.5 (6H, m), 1.3 (12H, m), 0.6 (9H, s), 0.5 (3H,
s), -0.2 (6H, s). 13C{1H} NMR (CD2Cl2): δ 152.0, 148.9, 140.8,
137.6, 38.3 (d, |J C-P| ) 52.0 Hz), 29.7, 28.6 (d, |J C-P| ) 15.9
Hz), 27.5, 15.4, 5.7, 3.8. 31P NMR (CD2Cl2): δ 57.1. 11B NMR
(CD2Cl2): δ -15.3. 27Al NMR (CD2Cl2): δ 59.2. 19F NMR (CD2-
Cl2): δ -55.9 (d, |J B-F| ) 23.1 Hz), -88.1 (t, |J B-F| ) 19.7 Hz),
-90.7 (t, |J B-F| ) 16.9 Hz).
(C6D6): δ 133.0, 132.3 (t, |J C-P| ) 3.2 Hz), 131.2, 128.3 (t, |J C-P
) 3.75 Hz), 41.8 (t, |J C-P| ) 69.8 Hz), 3.6. 31P NMR (C6D6): δ
32.4.
|
Syn th esis of [CH(P P h 2(NSiMe3))2]AlMe2 (20). To a solu-
tion of 17 (0.116 g, 0.206 mmol) in benzene was added Me2-
AlCl (1.0 M, 0.21 mL, 0.206 mmol). The mixture was stirred
for 12 h and filtered. The remaining solvent was removed
1
Syn th esis of [(P h 3P NSiMe3)AlMe2(P Me3)][MeB(C6F 5)3]
(29). To a solution of 27 (0.053 g, 0.06 mmol) in a 50/50
benzene/hexane solution was added PMe3 (0.006 mL, 0.06
mmol) in a similar solution. The reaction mixture was stirred
for 0.5 h and followed by decanting of the solvent. The
remaining solvent was removed under vacuum to yield a light
under vacuum to yield a white powder. Yield: 79%. H NMR
(C6D6): δ 7.6 (8H, m), 6.9 (12H, m), 3.5 (1H, t, |J P-H| ) 6.6
Hz), 0.2 (18H, s), 0.2 (6H, s). 13C{1H} NMR (C6D6): δ 136.5 (d,
|J C-P| ) 100.8 Hz), 132.3 (t, |J C-P| ) 4.1 Hz), 130.6,128.3, 25.2
(t, |J C-P| ) 122.1 Hz), 4.8. 31P NMR (C6D6): δ 28.7. Anal. Calcd
for C33H45P2N2Si2Al: C, 64.47; H, 7.38; N, 4.56. Found: C,
64.32; H, 7.27; N, 4.11.
1
yellow oil. H NMR (CD2Cl2): δ 7.7 (6H, m), 7.7 (9H, m), 0.9
(9H, d, |J P-H| ) 6.9 Hz), 0.5 (3H, s), 0.1 (9H, s), -0.7 (6H, s).
13C{1H} NMR (CD2Cl2): δ 150.2, 147.1, 139.5, 138.4, 136.2,
135.0 (d, |J C-P| ) 12.5 Hz), 133.9 (d, |J C-P| ) 10.2 Hz), 130.0,
126.9 (d, |J C-P| ) 99.9 Hz), 11.5 (d, |J C-P| ) 18.6 Hz), 4.2, 1.6,
1.6. 31P NMR (CD2Cl2): δ 33.9, -47.6. 11B NMR (CD2Cl2): δ
-15.3. 27Al NMR (CD2Cl2): δ 62.3. 19F NMR (CD2Cl2): δ -55.8
(d, |J B-F| ) 22.56), -88.0 (t, |J B-F| ) 20.59), -90.6 (t, |J B-F| )
21.7 Hz).
Syn th esis of [Me2Al(µ-NP t-Bu 3)2AlMe][MeB(C6F5)3] (30).
To a solution of B(C6F5)3 (0.066 g, 0.129 mmol) in a 50/50
benzene/hexane solution was added a solution of compound
14 (0.070 g, 0.129 mmol). The reaction mixture was stirred
for 0.5 h and followed by decanting of the solvent. The
remaining solvent was removed under vacuum to yield a light
Syn th esis of [CH(P P h 2(NSiMe3))2]MR2 (M ) Al, Bz, 21;
M ) Ga , R ) Me, 22; Bz, 23; R ) In , R ) Me, 24; Bz, 25).
These complexes were prepared in a similar manner employing
either benzylmagnesium bromide or methylmagnesium chlo-
ride, and thus only a single representative preparation is
described. To a solution of 17 (0.090 g, 0.137 mmol) in benzene
was added BzMgCl (1.0 M, 0.27 mL, 0.270 mmol). The mixture
was stirred for 12 h and filtered. The remaining solvent was
removed under vacuum to a yield white powder. (21) Yield:
1
81%. H NMR (C6D6): δ 7.5 (8H, m), 7.4 (4H, d, |J P-H| ) 7.7
Hz), 7.3 (4H, t, |J P-H| ) 7.5 Hz), 7.2 (2H, m), 7.0 (8H, m), 6.9
(4H, m), 3.0 (1H, t, |J P-H| ) 6.8), 2.5 (4H, s), 0.0 (18H, s). 13C-
{1H} NMR (C6D6): δ 148.5, 135.5 (d, |J C-P| ) 60.7 Hz), 132.3
(d, |J C-P| ) 6.2 Hz), 130.6, 129.6, 128.6, 128.1, 127.5, 121.9,
25.4 (t, |J C-P| ) 69.2 Hz), 5.1. 31P NMR (C6D6): δ 29.8. (22)
yellow oil. 1H NMR (CD2Cl2): δ 1.6 (3H, s), 1.5 (54H, d, |J H-H
|
) 13.5 Hz), 0.5 (3H, s), -0.2 (6H, s). 13C{1H} NMR (CD2Cl2):
δ 150.4, 147.2, 138.9, 135.6, 40.7 (d, |J C-P| ) 45.9 Hz), 31.7,
29.6, 10.0, 0.4. 31P NMR (CD2Cl2): δ 67.1. 11B NMR (CD2Cl2):
δ -15.3. 27Al NMR (CD2Cl2): δ 56.8. 19F NMR (CD2Cl2): δ
-55.8 (d, |J B-F| ) 22.6 Hz), -88.0 (t, |J B-F| ) 19.7 Hz), -90.6
(t, |J B-F| ) 19.7 Hz).
1
Yield: 86%. H NMR (C6D6): δ 7.6 (8H, m), 6.9 (12H, m), 3.4
(1H, br t), 0.4 (18H, s), -0.1 (6H, s). 13C{1H} NMR (C6D6): δ
135.5 (m), 132.1, 130.4, 128.1, 29.5 (t, |J C-P| ) 107.4 Hz), 4.8.
31P NMR (C6D6): δ 25.6. Anal. Calcd for C33H45P2N2Si2Ga: C,
60.28; H, 6.90; N, 4.26. Found: C, 60.02; H, 6.67; N, 4.08. (23)
1
Yield: 83%. H NMR (C6D6): δ 7.7 (8H, m), 7.5 (4H, m), 6.9
(12H, m), 6.8 (6H, m), 3.2 (1H, m), 2.1 (4H, s), 0.4 (18H, s).
13C{1H} NMR (C6D6): δ 146.3, 135.2 (d, |J C-P| ) 99.3 Hz),
132.2, 131.3, 128.7, 128.3, 128.0, 122.5, 70.6, 32.1 (t, |J C-P| )
Syn t h esis of [AlMe2(µ-NP t-Bu 3)2AlMe(P Me3)][MeB-
(C6F 5)3] (31). To a solution of 19 (0.070 g, 0.137 mmol) in CH2-
Cl2 was added PMe3 (0.005 mL, 0.137 mmol). The reaction
mixture was stirred for 0.5 h and followed by decanting of the
solvent. The remaining solvent was removed under vacuum
to yield a light-yellow oil. 1H NMR (CD2Cl2): δ 1.5 (57H, d,
|J P-H| ) 13.2 Hz), 1.3 (9H, d, |J P-H| ) 5.6 Hz), 0.5 (3H, s), -0.3
(6H, s). 13C{1H} NMR (CD2Cl2): δ 150.3, 147.2, 139.5, 138.5,
136.3, 135.3, 40.2 (d, |J C-P| ) 42 Hz), 30.7, 29.5, 14.9, 2.6. 31P
NMR (CD2Cl2): δ 65.4, -49.8. 11B NMR (CD2Cl2): δ -15.3.
27Al NMR (CD2Cl2): δ 60.5. 19F NMR (CD2Cl2): δ -55.7 (d,
1
102.7 Hz), 3.9. 31P NMR (C6D6): δ 25.4. (24) Yield: 78%. H
NMR (C6D6): δ 7.6 (8H, m), 7.0 (12H, m), 3.4 (1H, br t), 0.4
(18H, s), -0.2 (6H, s). 13C{1H} NMR (C6D6): δ 136.0, 132.2,
130.3, 128.0, 29.4 (t, |J C-P| ) 106.6 Hz), 5.1. 31P NMR (C6D6):
δ 25.6. Anal. Calcd for C33H45P2N2Si2In: C, 56.41; H, 6.46; N,
1
3.99. Found: C, 56.26; H, 6.23; N, 3.71. (25) Yield: 73%. H
NMR (C6D6): δ 7.3 (8H, m), 7.2 (8H, m), 7.1 (2H, m), 7.0 (12H,
m), 2.1 (4H, s), 3.2 (1H, m), 0.5 (18H, s). 13C{1H} NMR (C6D6):
δ 146.2, 136.4, 135.6, 132.2, 130.2, 128.7, 128.2, 127.3, 122.4,
28.6 (t, |J C-P| ) 108.1 Hz), 5.1. 31P NMR (C6D6): δ 25.4.
Syn th esis of [(R3P NSiMe3)AlMe2][MeB(C6F 5)3] (R )
i-P r , 26; P h , 27; Cy, 28). These compounds were prepared in
a similar fashion with the appropriate substitution of phos-
phinimine and aluminum reagent; thus, a single representa-
tive synthesis is detailed. To a solution of B(C6F5)3 (0.069 g,
0.134 mmol) in a 50/50 benzene/hexane solution was added 8
(0.043 g, 0.134 mmol) in a similar solution mixture. The
reaction mixture was stirred for 0.5 h and followed by
decanting of the solvent. The remaining solvent was removed
|J B-F| ) 23.1 Hz), -87.9 (t, |J B-F| ) 20.3 Hz), -90.5 (t, |J B-F
|
) 21.4 Hz).
X-r a y Da ta Collection a n d Red u ction . X-ray-quality
crystals of 1, 3, 6, 8, 13-15, 18, and 20 were obtained directly
from the preparation as described above. The crystals were
manipulated and mounted in capillaries in a glovebox, thus
maintaining a dry, O2-free environment for each crystal.
Diffraction experiments were performed on a Siemens SMART
System CCD diffractometer collecting a hemisphere of data
in 1329 frames with 10 s exposure times. Crystal data are
summarized in Table 1. The observed extinctions were con-
sistent with the space groups in each case. The data sets were
collected (4.5° < 2θ < 45-50.0°). A measure of decay was
obtained by recollecting the first 50 frames of each data set.
The intensities of reflections within these frames showed no
statistically significant change over the duration of the data
collections. The data were processed using the SAINT and
XPREP processing packages. An empirical absorption correc-
tion based on redundant data was applied to each data set.
Subsequent solution and refinement was performed using the
SHELXTL solution package operating on a SGI Challenge
mainframe computer with remote X-terminals or PC employ-
1
under vacuum to yield a light-yellow oil. (26) H NMR (CD2-
Cl2): δ 2.5 (3H, m), 1.3 (9H, d, |J H-H| ) 7.2 Hz), 1.4 (9H, d,
|J H-H| ) 7.2 Hz), 0.6 (9H, s), 0.5 (3H, s), -0.2 (6H, s). 13C{1H}
NMR (CD2Cl2): δ 150.2, 147.0, 138.8, 135.6, 25.6 (d, |J C-P| )
53.9 Hz), 17.3, 3.6, 10.1, 1.2. 31P NMR (CD2Cl2): δ 66.6. 11B
NMR (CD2Cl2): δ -15.3. 27Al NMR (CD2Cl2): δ 62.1. 19F NMR
(CD2Cl2): δ -55.8 (d, |J B-F| ) 23.1 Hz), -87.9 (t, |J B-F| ) 20.3
Hz), -90.6 (t, |J B-F| ) 21.2 Hz). (27) 1H NMR (CD2Cl2): δ 7.8
(6H, m), 7.7 (9H, m), 0.5 (3H, s), 0.2 (9H, s), -0.6 (6H, s). 13C-
{1H} NMR (CD2Cl2): δ 150.4, 147.2, 138.9, 133.9, 136.2, 132.4,
131.8, 125.1, 10.0, 2.5, 1.2. 31P NMR (CD2Cl2): δ 33.3. 11B NMR
(CD2Cl2): δ -15.3. 27Al NMR (CD2Cl2): δ 62.3. 19F NMR (CD2-
Cl2): δ -55.9 (d, |J B-F| ) 22.9 Hz), -88.0 (t, |J B-F| ) 20.8 Hz),
2
2
ing X-emulation. The reflections with Fo > 3σFo were used
in the refinements.