4488 Organometallics, Vol. 28, No. 15, 2009
Semproni et al.
(dd, 2JHH=18.4, 5.9, 1H, CCH2CH), 5.26 (m, 1H, CHMe), 5.39
(m, 1H, CHCH2), 6.88 (m overlapping, 3H, aryl CH). 13C{1H}
NMR (150 MHz, C6D6): δ 2.5 (CH2SiMe3), 3.8 (CH2SiMe3), 10.6
(C5Me5), 18.9 (CHCH3), 19.4 (aryl CH3), 37.4 (CH2CH), 108.3
(C5Me5), 123.0 (CH2CH), 126.8 (Ar C), 129.6 (Ar C), 130.6 (Ar C),
131.0 (Ar C), 138.4 (Ar C), 156.6 (CHCH), 214.8 (CNCH). MS
(LREI, m/z, probe temperature 100 °C): 622 [Pþ, 184W].
1H, benzyl CH2), 6.45 (d, 3JHH=15.3, 1H, NCCH), 6.88 (m, 1H,
CH2CHCH), 7.00-7.41 (m, 8H, aryl CH). 13C{1H} NMR (150
MHz, C6D6): δ 10.6 (C5Me5), 12.8 (CH2Me), 18.4 (ArMe), 19.6
(ArMe), 27.0 (MeCH2), 34.8 (CH2C6H5), 108.4 (C5Me5), 122.2
(CHCHCN), 126.6 (Ar C), 127.4 (Ar C), 129.7 (Ar C), 131.4 (Ar
C), 132.9 (Ar C), 152.9 (Ar C), 157.9 (CHCN), 214.7 (NC). MS
(LREI, m/z, probe temperature 100 °C): 626 [Pþ, 184W]. MS
(HREI, m/z, probe temperature 120 °C): Pþ calcd for
C30H38N2OW: 626.24937, found 626.24936.
Preparation of Cp*W(NO)(CH2SiMe3)(η2-CH3CH2CHCH-
CdNC6H3Me2) (4b). A sample of 1 (24.0 mg, 0.049 mmol) was
dissolved in MeCN (0.5 mL) in a 4-dram vial to obtain a yellow
solution. To this was added dropwise a solution of CNC6H3Me2
(6.0 mg, 0.046 mmol) in MeCN (0.25 mL), and the mixture was
placed in the freezer for 1 h. The mixture was then transferred to
the top of an alumina I column (0.5 ꢀ 5 cm), the column was
eluted with 4:1 pentane/Et2O, and the dark orange band that
developed was collected. The solvent was removed from the
eluate in vacuo, and the residue was redissolved in a minimum
amount of Et2O. The Et2O solution was stored overnight at
-30 °C to induce the deposition of 4b as irregularly shaped red
crystals (19.0 mg, 79% yield).
Preparation of Cp*W(NO)(CH2C6H5)(η2-CH3CH2CHCH-
CdNC4H9) (6b). A sample of 2 (19.0 mg, 0.038 mmol) was
dissolved in Et2O (1 mL) and THF (5 mL) in a 4-dram vial to
obtain an orange solution. To this solution was added a solution
of C4H9NC (11.0 mg, 0.133 mmol) in Et2O (1 mL). After 20 h,
the final orange solution was transferred to the top of an
alumina I column (0.5 ꢀ 6 cm). The column was eluted with
Et2O, and the yellow band that developed was collected. The
solvent was removed from the eluate in vacuo, to obtain 6b as a
viscous red oil (14.0 mg, 74% yield).
1
IR: νNO 1548 cm-1. H NMR (400 MHz, C6D6): δ 0.79 (m
Anal. Calcd for C27H42N2OSiW: C, 52.09; H, 6.80; N, 4.50.
Found: C, 52.16; H, 6.78; N, 4.48. IR: νNO 1554 cm-1. 1H NMR
(400 MHz, C6D6): δ -0.30 (d, 2JHH=13.5, 1H, CH2SiMe3), 0.21
(d, 2JHH=13.5, 1H, CH2SiMe3), 0.35 (s, 9H, CH2SiMe3), 0.73 (t,
3JHH=14.9, 3H, CH2CH3), 1.79 (m, 2H, CH2CH3), 1.81 (s, 15H,
C5Me5), 2.05 (s, 6H, aryl CH3), 6.30 (d, 3JHH=15.5, 1H, NCCH),
6.84 (m, 3JHH=15.3, 6.9, 6.5, 1H, CHCH), 6.9-6.95 (m, 3H, aryl
H). 13C{1H} NMR (150 MHz, C6D6): δ 2.9 (CH2SiMe3), 3.8
(CH2SiMe3), 10.8 (C5Me5), 12.8 (CH2CH3), 19.2 (aryl CH3),
27.1 (CH2CH3), 108.5 (C5Me5), 122.3 (CCH), 127.1 (Ar C),
130.0 (Ar C), 131.4 (Ar C), 132.3 (Ar C), 138.4 (Ar C), 156.6
(CHCH), 214.8 (CNCH). MS (LREI, m/z, probe temperature
100 °C): 622 [Pþ, 184W].
overlapping, 6H, butyl CH3 and CHCH2CH3), 1.07 (m, 2H, butyl
CH2), 1.29 (m, 2H, butyl CH2), 1.72 (s, 15H, C5Me5), 1.88 (t,
2
3JHH =7.0, 2H, CHCH2CH3), 2.71 (d, JHH =10.6, 1H, benzyl
CH2), 2.94 (d, 2JHH=10.6, benzyl CH2), 2.96 (m overlapping, 2H,
NCH2CH2), 6.36 (d, JHH=14.9, 1H, NCCH), 6.82 (dt, JHH=
3
3
15.2, 6.5, 1H, CH2CHCH), 6.95 (t, 3JHH=7.2, 1H, para aryl CH),
3
3
7.25 (t, JHH=7.4, 2H, meta aryl CH), 7.83 (d, JHH=7.4, 2H,
ortho aryl CH). 13C{1H} NMR (150 MHz, C6D6): δ 10.4 (C5Me5),
12.7 (MeCH2CH), 14.3 (MeCH2), 21.1 (MeCH2CH2), 27.1
(MeCH2CH), 32.3 (CH2CH2), 32.8 (CH2C6H5), 44.2 (NCH2),
108.1 (C5Me5), 123.0 (CHCHCN), 128.3 (Ar C), 128.7 (Ar C),
129.8 (Ar C), 154.7 (Ar (i) C), 157.8 (CHCN), 208.1 (CN). MS
(LREI, m/z, probe temperature 100 °C): 578 [Pþ, 184W]. MS
(HREI, m/z, probe temperature 100 °C): Pþ calcd for
C26H38N2OW 578.24910, found 578.24937.
Preparation of Cp*W(NO)(CH2C6H5)(η2-CH3CHCHCH2-
CdNC6H3Me2) (5a). A sample of 2 (19.0 mg, 0.039 mmol)
was dissolved in THF (2 mL) in a 4-dram vial to obtain an
orange solution. To this solution was added dropwise a solution
of CNC6H3Me2 (16.0 mg, 0.124 mmol) in THF (1 mL), and the
mixture was left to sit for 20 h. The solvent was removed from
the red-orange solution in vacuo, and the residue was recrys-
tallized from Et2O at -30 °C to obtain 5a as irregularly shaped,
orange-brown crystals (15.0 mg, 79% yield).
Preparation of Cp*(W)(NO)(C(O)Me)(η3-CH2CHCHMe)
(7). A sample of 1 (97.0 mg, 0.198 mmol) was dissolved in C6H6
(6 mL) in a Schlenk tube. The yellow solution was cannulated into
a stainless steel pressure vessel containing additional C6H6 (12
mL). The vessel was pressurized with 1000 psig of CO gas, and the
solution was stirred for 72 h. The pressure was then released, and
the solution was transferred by pipet to a Schlenk tube. The
solvent was removed in vacuo, the yellow residue was dissolved in
pentane, and this solution was transferred to the top of an alumina
I column (2 ꢀ 5 cm). The column was eluted with 4:1 pentane/
Et2O, and the yellow band that developed was collected. The
volume of the eluate was reduced in vacuo, and the concentrated
solution was stored at -30 °C overnight to induce the deposition
of 7 as yellow prisms (51 mg, 53% yield).
IR: νNO 1560 cm-1. 1H NMR (400 MHz, C6D6): δ 1.71 (s, 3H,
aryl Me), 1.77 (s, 3H, aryl Me), 1.86 (d, 3JHH=9.0, 3H, MeCH)
2.05 (s, 15H, C5Me5), 2.41 (d, 2JHH=10.6, 1H, benzyl CH2), 2.69
(d, 2JHH=10.6, 1H, benzyl CH2), 2.78 (dd, 2JHH=17.8, 6.5, 1H,
NCCH2), 3.33 (dd, 2JHH=18.0, 6.3, 1H, NCCH2), 5.23 (m, 1H,
MeCH), 5.38 (m, 1H, MeCHCH), 6.95-7.35 (m, 8H, aryl CH).
13C{1H} NMR (150 MHz, C6D6): δ 10.8 (C5Me5), 18.4 (Me),
18.6 (Me), 19.2 (Me), 36.0 (CH2C6H5), 110.0 (C5Me5), 122.3
(CH2CH), 126.4 (Ar C), 127.4 (Ar C), 127.8 (Ar C), 128.7 (Ar C),
130.0 (Ar C), 130.6 (Ar C), 136.2 (CHMe), 153.0 (Ar (i) C), 221.4
(NC). MS (LREI, m/z, probe temperature 100 °C): 626 [Pþ,
184W]. MS (HREI, m/z, probe temperature 120 °C): Pþ calcd for
C30H38N2OW 626.24937, found 626.24936.
1
IR: νNO 1594 cm-1, νCO 1615 cm-1. H NMR (400 MHz,
C6D6): δ 1.28 (m obscured, 1H, allyl CHMe), 1.63 (s, 15H,
3
C5Me5), 1.65 (d obscured, 2H, allyl CH2), 1.91 (d, JHH=5.5,
3H, CHMe), 2.50 (s, 3H, C(O)Me), 4.57 (ddd, 3JHH=13.8, 9.9,
7.2, 1H, allyl CH). 13C{1H} NMR (150 MHz, C6D6): δ 10.3
(C5Me5), 17.9 (allyl Me), 46.4 (C(O)Me), 61.1 (MeCHCH), 66.1
(CH2CH), 108.7 (C5Me5), 111.1 (MeCHCH), 258.6 (C(O)Me).
MS (LREI, m/z, probe temperature 100 °C); 447 [Pþ, 184W].
Preparation of Cp*(W)(NO)(C(O)CH2CMe3)(η3-CH2CHC-
HMe) (8). In a glovebox, a sample of Cp*(W)(NO)(CH2CMe3)-
(η3-CH2CHCHMe)6 (65.0 mg, 0.137 mmol) was dissolved in
pentane (6 mL) in a 4-dram vial. The orange solution was
transferred to a stainless steel pressure vessel. The vessel was
pressurized with 850 psig of CO gas, and the solution was stirred
for 20 h. The pressure was then released, the solvent was
removed in vacuo, and the vessel was brought into the glovebox.
The yellow residue was dissolved in pentane and transferred to
the top of a Celite column (2 ꢀ 3 cm). The column was eluted
with pentane, and the orange band that developed was collected.
The eluate was taken to dryness in vacuo, and the residue was
redissolved into a minimal amount of pentane. Slow evaporation
Preparation of Cp*W(NO)(CH2C6H5)(η2-CH3CH2CHCH-
CdNC6H3Me2) (5b). A sample of 2 (25.0 mg, 0.051 mmol)
was dissolved in Et2O (5 mL) in a 4-dram vial to obtain an
orange solution. To this solution was added dropwise a solution
of CNC6H3Me2 (8.0 mg, 0.062 mmol) in Et2O (1 mL). After
20 h, the final red solution was transferred to the top of an
alumina I column (0.5 ꢀ 5 cm). The column was eluted with
Et2O, and the red band that developed was collected. The
solvent was removed from the eluate in vacuo, and the residue
was recrystallized from Et2O at -30 °C to obtain 5b as plate-like
red crystals (18.0 mg, 72% yield).
1
IR: νNO 1560 cm-1. H NMR (400 MHz, C6D6): δ 0.87 (t,
3JHH = 7.4, 3H, MeCH2CH), 1.57 (s, 3H, aryl Me), 1.92 (m
overlapping, 2H, MeCH2CH), 1.99 (s, 15H, C5Me5), 2.09 (s, 3H,
aryl Me), 2.75 (d, 2JHH=10.2, 1H, benzyl CH2), 2.98 (d, 2JHH=10.2,