2384 Inorganic Chemistry, Vol. 36, No. 11, 1997
Galindo et al.
Et2O (20 mL). The solution was stirred for 10 min. The solvent was
removed in vacuo and the red oil obtained was extracted with Et2O
and concentrated in vacuo. Cooling the solution at -20 °C afforded
compound 4 as a crystalline red solid. The reaction was quantitative
Experimental Section
Microanalyses were carried out by the Microanalytical Service of
the University of Sevilla. Infrared spectra were recorded on a Perkin-
Elmer Model 684 or 883 spectrophotometer. 1H, 13C, and 31P NMR
spectra were run on Bruker AMX-300 and Bruker AMX-500 spec-
trometers. 31P shifts were measured with respect to external 85%
H3PO4. 13C NMR spectra were referenced using the 13C resonance of
the solvent as an internal standard but are reported with respect to
SiMe4. Magnetic moments were measured in solution by the Evans
method21 or in the solid state with a Sherwood Scientific (Cambridge
Research Laboratory) magnetic balance. All preparations and other
operations were carried out under oxygen-free nitrogen following
conventional Schlenk techniques. Solvents were dried and degassed
before use. The petroleum ether used had bp 40-60 °C. The
by NMR. 31P{1H} NMR (C6D6): AX2 spin system, δ 125.0 (t, 2JAX
)
148 Hz), 117.1 (d). 1H NMR (C6D6): δ 14.5 (br, 1, OH), 6.55 (s, 4,
CH, Ph), 5.15 (s, 5, Cp), 4.35, 4.23 (br, 6, CH2), 2.60 (s, 12, CH3 ortho),
2.05 (s, 6, CH3 para), 1.2 (br m, 18, CH3). 13C{1H} NMR (C6D6): δ
153.0 (C ipso), 138.7 (C para), 135.7 (C ortho), 128.6 (C meta), 90.2
(Cp), 62.8 (br m, CH2), 20.7 (CH3 para), 18.5 (CH3 ortho), 16.5 (br,
CH3). Anal. Calcd for C35H58N2Cl2CoMoO9P3: C, 43.3; H, 6.0; N,
2.9. Found: C, 42.8; H, 6.3; N, 2.5.
Mo(Nmes)2(acac)2 (5). A mixture of MoCl2(Nmes)2(dme) (0.52 g,
1 mmol) and Tl(acac) (0.61 g, 2 mmol) in THF (50 mL) was stirred at
ambient temperature for 6 h. After removal of the solvent under
vacuum the resulting residue was dissolved in petroleum ether (60 mL)
and filtered to separate the TlCl. The filtrate was concentrated and
cooled to -20 °C. Compound 5 was obtained as a brown solid (0.36
g, 66%). 1H NMR (C6D6): δ 6.68 (s, 4, CH, Ph), 5.28 (s, 2, CH,
acac), 2.51 (s, 12, CH3 ortho), 2.10 (s, 6, CH3 para), 1.82, 1.74 (s, 6,
CH3, acac). 13C{1H} NMR (C6D6): δ 191.6, 185.6 (CO, acac), 156.1
(C ipso), 133.2 (C para), 129.8 (C ortho), 128.0 (C meta), 101.8 (CH,
acac), 27.2, 26.2 (CH3, acac), 20.7 (CH3 para), 18.5 (CH3 ortho). Anal.
Calcd for C28H36N2MoO4: C, 60.0; H, 6.4; N, 5.0. Found: C, 60.0;
H, 6.8; N, 4.5.
MoCl2(Nmes)(O)(dme) (6). A suspension of MoCl2(Nmes)2(dme)
(0.79 g, 1.5 mmol) and MoCl2(O)2(dme) (0.44 g, 1.5 mmol) in dme
(35 mL) was heated at reflux, under nitrogen, for 6 h. The solution
was cooled to ambient temperature and then evaporated to dryness.
The residue was dissolved in Et2O (120 mL), filtered, concentrated
under reduced pressure, and cooled at -20 °C. Compound 6 was
obtained as a microcrystalline red solid (0.72 g, 59%). 1H NMR
(C6D6): δ 6.51 (s, 2, CH, Ph), 3.44 (br, 6, CH3O), 3.12 (br, 4, OCH2),
2.86 (s, 6, CH3 ortho), 2.04 (s, 3, CH3 para). 13C{1H} NMR (C6D6):
δ 153.2 (C ipso), 139.5 (C para), 138.3 (C ortho), 128.4 (C meta),
70.7 (br, OCH2), 63.0 (br, CH3O), 20.7 (CH3 ortho), 18.4 (CH3 para).
Anal. Calcd for C13H21NCl2MoO3: C, 38.4; H, 5.2; N, 3.5. Found:
C, 38.4; H, 5.2; N, 3.1.
33
compounds MoCl4(THF)2 and MoCl2(O)2(dme)34 were prepared
according to the literature procedures. (NH4)2Mo2O7 was purchased
from commercial sources and used as received.
MoCl2(Nmes)2(dme) (1). A solution of (NH4)2Mo2O7 (4.9 g, 14.5
mmol) in 80 mL of dimethoxyethane (dme) was reacted with 8 equiv
of NEt3 dissolved in dme (10 mL), ClSiMe3 (17 equiv) also in 10 mL
of dme, and a solution of 2,4,6-trimethylphenylamine (58 mmol) in
dme (10 mL). A condenser was attached to the reaction vessel, and
the orange suspension was heated at reflux for 8 h, during which time
the reaction mixture turned red. The ammonium salts were eliminated
by filtration, the volatiles were pumped off under vacuum, and the
residue was washed with petroleum ether and dried in vacuo. The
resulting red solid was extracted with Et2O. Cooling to -30 °C afforded
red crystals of 1 (7.5 g, 50%). 1H NMR (C6D6): δ 6.56 (s, 4, CH,
Ph), 3.38 (br, 6, CH3O), 3.30 (br, 4, OCH2), 2.66 (s, 12, CH3 ortho),
2.02 (s, 6, CH3 para). 13C{1H} NMR (C6D6): δ 154.9 (C ipso), 137.0
(C para), 134.3 (C ortho), 129.4 (C meta), 71.9 (OCH2), 62.0 (CH3O),
21.1 (CH3 para), 18.5 (CH3 ortho). Anal. Calcd for C21H32N2Cl2-
MoO2: C, 50.5; H, 6.1; N, 5.4. Found: C, 50.1; H, 6.5; N, 5.4.
(LOEt)Mo(Nmes)2Cl (2). A reaction flask was charged with MoCl2-
(Nmes)2(dme) (0.6 g, 1.1 mmol) and NaLOEt (0.58 g, 1.1 mmol). A
50 mL volume of THF was added, and the red solution was stirred at
ambient temperature overnight. Volatiles were removed; the residue
was extracted with Et2O (20 mL), and filtered to remove NaCl.
Concentration of the solution, addition of 10 mL of petroleum ether,
(LOEt)Mo(Nmes)(O)Cl (7). To a mixture of MoCl2(Nmes)(O)(dme)
(0.10 g, 0.25 mmol) and NaLOEt (0.14 g, 0.25 mmol) was added THF
(25 mL). The resulting orange solution was stirred at ambient
temperature overnight. The solvent was pumped off and Et2O (50 mL)
was added to dissolve the orange residue. Following filtration, the
resulting solution was concentrated and cooled at -20 °C, giving 7 as
a red crystalline solid (0.12 g, 60%). 31P{1H} NMR (C6D6): δ 124.1
(br t, JPP ) 156 Hz), 112.8 (br t, JPP ) 156 Hz), 111.1 (br t, JPP ) 156
Hz). 1H NMR (C6D6): δ 6.66 (s, 2, CH, Ph), 4.83 (s, 5, Cp), 4.44 (m,
6, CH2), 4.10 (m, 4, CH2), 3.89 (m, 2, CH2), 3.06 (s, 6, CH3 ortho),
and cooling to -20 °C afforded red crystals of compound 2 (0.67 g,
60%). 31P{1H} NMR (C6D6): AX2 spin system, δ 109.7 (d, JPP
)
2
158 Hz), 122.8 (t). 1H NMR (C6D6): δ 6.70 (s, 4, CH, Ph), 4.88 (s,
5, Cp), 4.51, 4.18, 4.00 (m, 4, CH2), 2.74 (s, 12, CH3 ortho), 2.11 (s,
6, CH3 para), 1.30, 1.15, 1.07 (t, 3JHH ) 7 Hz, 6, CH3). 13C{1H} NMR
(C6D6): δ 155.8 (C ipso), 133.0 (C para), 131.7 (C ortho), 128.1 (C
meta), 89.1 (Cp), 62.2 (m, CH2), 61.0 (br d, CH2), 60.8 (br d, CH2),
20.7 (CH3 para), 18.8 (CH3 ortho), 16.6, 16.4, 16.3, 16.2 (CH3). Anal.
Calcd for C35H57N2ClCoMoO9P3: C, 45.0; H, 6.1; N, 3.0. Found: C,
44.6; H, 6.2; N, 3.0.
3
2.12 (s, 3, CH3 para), 1.25, 1.22, 1.21, 1.12, 1.07, 0.91 (t, JHH ) 7
Hz, 3, CH3). 13C{1H} NMR (C6D6): δ 153.6 (C ipso), 138.4 (C para),
136.9 (C ortho), 128.0 (C meta), 89.0 (Cp), 62.2, 61.8, 61.8, 61.4, 60.6
(d, JCP ) 9 Hz, CH2), 20.8 (CH3 para), 18.4 (CH3 ortho), 16.6, 16.4,
16.3, 16.1 (d, JCP ) 6 Hz, CH3). Anal. Calcd for C26H46-
NClCoMoO10P3: C, 38.3; H, 5.6; N, 1.7. Found: C, 38.1; H, 5.7; N,
1.7.
TpMo(Nmes)2Cl (3). To a mixture of MoCl2(Nmes)2(dme) (0.3 g,
0.57 mmol) and KTp (0.14 g, 0.57 mmol) was added THF (35 mL).
The brown solution was stirred at room temperature for 1 day, and the
volatiles were removed under reduced pressure. The brown residue
was extracted with Et2O and filtered to remove KCl. The filtrate was
concentrated and cooled to -20 °C. Green crystals of 3 were obtained
in 55% yield. 1H NMR (C6D6): δ 8.23 (d, 3JHH ) 1.9 Hz, 2, CH, pz),
7.34 (d, 3JHH ) 2.2 Hz, 1, CH, pz), 7.25 (t, 3JHH ) 2.2 Hz, 3, CH, pz),
TpMo(Nmes)(O)Cl (8). A solution of MoCl2(Nmes)(O)(dme) (0.16
g, 0.39 mmol) and KTp (0.10 g, 0.6 mmol) in THF (25 mL) was stirred
at room temperature for 1 day. After the volatiles were removed, an
orange solid was obtained. Dissolution in Et2O, filtration, and cooling
at -20 °C afforded orange crystals of 8 (0.09 g, 47%). 1H NMR
6.62 (s, 4, CH, Ph), 5.75 (t, 3JHH ) 1.9 Hz, 2, CH, pz), 5.58 (t, 3JHH
)
2.2 Hz, 1, CH, pz), 2.30 (s, 12, CH3 ortho), 2.08 (s, 6, CH3 para).
13C{1H} NMR (C6D6): δ 154.3 (C ipso), 144.4, 143.9, 136.0 (C, pz),
135.3 (C para), 133.6 (C, pz), 133.3 (C ortho), 128.6 (C meta), 105.6,
105.1 (C, pz), 20.6 (CH3 para), 18.7 (CH3 ortho). Anal. Calcd for
C27H32N8ClBMo: C, 53.1; H, 5.2; N, 18.4. Found: C, 53.5; H, 5.5;
N, 18.0.
(η2-HLOEt)Mo(Nmes)2Cl2 (4). A solution of HCl in Et2O (10 mL),
prepared in situ from ClSiMe3 (0.2 mL, excess) and MeOH (1 mL),
was added to a solution of (LOEt)Mo(Nmes)2Cl (0.10 g, 0.1 mmol) in
3
(C6D6): δ 8.42, 8.00, 7.77, 7.67, 7.64, 7.54 (d, JHH ) 2 Hz, 1, CH,
3
pz), 6.86 (s, 2, Ph), 6.31, 6.19, 6.18 (t, JHH ) 2 Hz, 1, CH, pz), 2.48
(s, 6, CH3 ortho), 2.40 (s, 3, CH3 para). 13C{1H} NMR (CDCl3): δ
152.6 (C ipso), 144.1, 143.6, 143.0, 141.5 (C, pz), 141.4 (C para), 136.7
(C ortho), 134.7, 134.3 (C, pz), 128.5 (C meta), 106.5, 105.7, 105.2
(C, pz), 21.4 (CH3 para), 18.4 (CH3 ortho). Anal. Calcd for
C18H21N7ClBMoO: C, 43.8; H, 4.3; N, 19.9. Found: C, 43.5; H, 4.5;
N, 19.6.
(CpTMS)Mo(Nmes)(O)Cl (9). To a solution of MoCl2(Nmes)(O)-
(dme) (0.43 g, 1.06 mmol) in THF (35 mL) was added a 0.31 M THF
solution of NaCpTMS (3.42 mL, 1.06 mmol). The color of the
suspension changed from red to brown, and the reaction mixture was
(33) Dilworth, J. R.; Richards, R. L. Inorg. Synth. 1980, 20, 119.
(34) This complex was prepared by a modification of the experimental
procedure reported in: Kamenar, B.; Penavic, M.; Korpar-Colig, B.;
Markovic, B. Inorg. Chim. Acta 1982, 65, L245.