Inorganic Chemistry
Article
the filtrate under vacuum yielded compound 2b as a brown solid
dichloromethane (10 mL), and the mixture was stirred at room
temperature for 5 min to give a cherry red solution. The solvent was
then removed under vacuum and the residue was washed with
petroleum ether (4 × 5 mL) to yield a cherry red solid shown by
(
0.213 g, 64%). In solution, this compound displays two isomers (A
and B), with an equilibrium A/B ratio of ca. 5/1 in CD Cl at room
2
2
temperature. Anal. Calcd for C H BF N O PW : C, 32.10; H, 3.59;
2
4
32
4
2
4
2
−
N, 3.12. Found: C, 31.82; H, 3.65; N, 2.81. ν(CO) (CH Cl ): 2017
NMR to contain a mixture of nitroxyl complex 3b (CF SO salt, δP
2
2
3
3
(
(
s), 1981 (w, sh); ν(NO) (CH Cl ): 1665 (vs). ν(CO) (THF): 2012
166.4, JPW = 313, 219) and two isomers (A and B) of nitrosomethane
complex 4b, in a ratio of ca. 6:7:2 respectively. Attempts to further
purify compound 4b were unsuccessful. Data for isomer A: H NMR:
2
2
s), 1980 (m); ν(NO) (THF): 1681 (vs), 1657 (s). Data for Isomer
1
1
A: H NMR: δ 6.06 (s, 10H, Cp), 3.10−0.20 (m, 22H, Cy). Data for
1
Isomer B: H NMR: δ 6.10, 5.88 (2s, 2 × 5H, Cp), 3.10−0.20 (m,
δ 6.28, 6.275 (2s, 2 × 5H, Cp), 4.08 (d, J = 1, 3H, NMe), 2.75−
PH
1
2
2H, Cy).
1.20 (m, 22H, Cy). Data for isomer B: H NMR: δ 6.49, 6.30 (2s, 2 ×
1
2
Preparation of [Mo Cp (μ-PCy )(μ-κ :η -HNO)(NO) ](BF )
5H, Cp), 3.75 (d, JPH = 2, 3H, NMe), 2.75−1.20 (m, 22H, Cy). NMR
2
2
2
2
4
(3a). Solid [FeCp ](BF ) (0.018 g, 0.066 mmol) was added to a
2 4
dichloromethane solution (10 mL) of compound 1a (0.040 g, 0.066
mmol), and the mixture was stirred at room temperature for 5 min to
give a red solution. After removal of solvent under vacuum, the
residue was washed with petroleum ether (4 × 7 mL) to remove
ferrocene, then dissolved in dichloromethane and filtered. Removal of
solvent from the filtrate yielded compound 3a as a red solid (0.038 g,
Preparation of [Mo Cp (μ-PCy )(μ-NH )(NO) ] (5a). A tetrahy-
2
2
2
2
2
drofuran solution (10 mL) of compound 1a (0.050 g, 0.082 mmol)
was stirred vigorously with Na(Hg) (1 mL of a 0.5% amalgam, 1.03
mmol) for 10 min to give a brown solution. The solvent was then
removed from the solution under vacuum, the residue extracted with
dichloromethane/petroleum ether (1/2), and the extracts chromato-
graphed on an alumina column at 288 K. Elution with dichloro-
methane/petroleum ether (2/1) gave a yellow fraction yielding, after
removal of solvents, compound 5a as a yellow solid (0.015 g, 31%).
Spectroscopic and microanalytical data for this product were identical
to the product obtained from 1a and Zn(Hg) (see ref 11).
8
3%). Spectroscopic and microanalytical data for this product were
identical to the product obtained from 1a and HBF ·OEt (see ref
1
4
2
1).
Preparation of [W Cp (μ-PCy )(μ-κ :η -HNO)(NO) ](BF ) (3b).
1
2
2
2
2
2
4
Solid [FeCp ](BF ) (0.012 g, 0.044 mmol) was added to a
2
4
dichloromethane solution (10 mL) of compound 1b (0.030 g,
.038 mmol), and the mixture was stirred at room temperature for 5
0
Preparation of [W Cp (μ-PCy )(μ-NH )(NO) ] (5b). A tetrahy-
2
2
2
2
2
min to give a brown solution. After removal of solvent under vacuum,
the residue was washed with petroleum ether (4 × 7 mL), then
dissolved in dichloromethane and filtered. Removal of solvent from
the filtrate yielded compound 3b as a brown solid (0.028 g, 84%).
Anal. Calcd for C H BF N O PW : C, 30.27; H, 3.81; N, 4.81.
drofuran solution (10 mL) of compound 1b (0.030 g, 0.038 mmol)
was stirred vigorously with Na(Hg) (1 mL of a 0.5% amalgam, 1.03
mmol) for 5 min to give a yellow solution which was separated from
the amalgam by transferring it to an empty Schlenk tube using a
cannula. The solvent was then removed from the solution under
vacuum, the residue extracted with toluene, and the extracts filtered.
Removal of solvent from the filtrate gave compound 5b as a yellow
solid (0.010 g, 34%). Anal. Calcd for C H N O PW : C, 34.26; H,
22
33
4
3
3
2
1
Found: C, 29.95; H, 3.53; N, 4.38. H NMR: δ 10.98 (s, br, 1H, NH),
.85, 5.81 (2s, 2 × 5H, Cp), 2.30−1.00 (m, 22H, Cy).
5
1
2
Preparation of [Mo Cp (μ-PCy )(μ-κ :η -MeNO)(NO) ](BAr′ )
2
2
2
2
4
22 34
3
2
2
1
(4a). Solid [Me O](BF ) (0.015 g, 0.101 mmol) was added to a
4.44; N, 5.45. Found: C, 33.95; H, 4.07; N, 5.13. H NMR: δ 5.69 (s,
3
4
solution of compound 1a (0.040 g, 0.066 mmol) in dichloromethane
10 mL) at 273 K, and the mixture was stirred at this temperature for
h to give a red solution shown by NMR to contain a mixture of
nitroxyl complex 3a and two isomers of the nitrosomethane complex
10H, Cp), 3.19 (s, br, 2H, NH ), 2.25−1.10 (m, 22H, Cy).
2
(
1
Preparation of cis-[Mo Cp (μ-PCy )(μ-NH )(NO) ] (cis-5a). A
2
2
2
2
2
tetrahydrofuran solution (10 mL) of compound cis-1a (0.030 g, 0.049
mmol) was stirred vigorously with Na(Hg) (1 mL of a 0.5% amalgam,
1.03 mmol) for 20 min to give a yellow solution. Workup as described
for 5a yielded compound cis-5a as a yellow solid (0.015 g, 51%). Anal.
Calcd for C H Mo N O P: C, 44.38; H, 5.76; N, 7.06. Found: C,
1
2
[
Mo Cp (μ-PCy )(μ-κ :η -MeNO)(NO) ](BF ) (A, δ 256.1, and B,
2 2 2 2 4 P
δP 251.1), in a ratio of ca. 5:6:2, respectively. The solution was then
allowed to reach room temperature, solid Na(BAr ′) (0.059 g, 0.067
4
22 34
2
3
2
mmol) added, and the mixture stirred for 5 min. The solvent was then
removed under vacuum, the residue extracted with dichloromethane/
petroleum ether (1/2), and the extracts chromatographed on an
alumina column at 253 K. Elution with dichloromethane/petroleum
ether (1/1) gave a blue fraction containing a small amount of
compound 1a. Elution with dichloromethane/petroleum ether (2/1)
gave a rose fraction yielding, after removal of solvents, compound 4a
as a rose solid (0.020 g, 31%). This solid was shown by NMR to
contain a mixture of two isomers A and B in a ratio of ca. 2/1. Anal.
Calcd for C H BF Mo N O P: C, 44.41; H, 3.18; N, 2.82. Found:
43.95; H, 5.49; N, 6.84. ν(NH) (Nujol): 3368 (w), 3270 (w); ν(NO)
1
(Nujol): 1578 (vs), 1536 (s). H NMR: δ 5.45 (s, 10H, Cp), 3.84,
3.21 (2s, br, 2 × 1H, NH ), 2.45−1.10 (m, 22H, Cy).
2
Preparation of [Mo Cp (μ-PCy ){μ-NP(OEt) }(NO) ] (6). Neat
2
2
2
3
2
P(OEt) (300 μL, 1.749 mmol) was added to a toluene solution (10
3
mL) of compound 1a (0.030 g, 0.049 mmol), and the mixture was
refluxed for 20 h to give a yellow solution. After removal of the solvent
under vacuum, the residue was extracted with dichloromethane/
petroleum ether (1/2) and the extracts chromatographed on an
alumina column at 253 K. Elution with dichloromethane/petroleum
ether (1/2) gave a yellow fraction yielding, after removal of solvents,
5
5
47
24
2
3
3
1
C, 44.20; H, 3.12; N, 2.67. Data for isomer A: H NMR: δ 7.72 (m,
H, C H ), 7.56 (m, 4H, C H ), 6.04, 5.75 (2s, 2 × 5H, Cp), 4.00 (d,
3
1
1
8
essentially pure compound 6 as a yellow oil (0.020 g, 53%). P{ H}
6
2
6
2
1
3
1
1
JPH = 2, 3H, NMe), 2.80−0.60 (m, 22H, Cy). C{ H} NMR: δ 162.2
NMR: δ 215.3 (s, μ-PCy ), 26.9 [s, μ-NP(OPh) ]. H NMR: δ 5.59
2
3
1
2
[
=
q, JCB 3= 50, C (C H )], 135.2 [s, C (C H )], 129.3 [qq, J = 31, JCB
(s, 10H, Cp), 4.03, 3.83 (2m, 2 × 3H, OCH ), 2.50−1.15 (m, 22H,
6
2
6
2
CF
2
3, C (C H )], 125.0 [q, J = 272, CF ], 117.9 [septet, J = 3,
6
2
CF
3
CF
4
C (C H )], 103.0, 102.8 [2s, Cp], 68.1 [s, NMe], 50.2 [d, J = 13,
C (Cy)], 49.8 [d, J = 10, C (Cy)], 35.1 [d, J = 6, C (Cy)], 35.0
d, J = 5, 2C (Cy)], 34.4 [d, J = 2, C (Cy)], 28.4, 28.3 [d, J =
6
2
CP
1
1
2
Reaction of cis-1a with P(OPh) . Neat P(OPh) (100 μL, 0.382
CP
CP
3
3
2
2
[
mmol) was added to a toluene solution (10 mL) of compound cis-1a
(0.050 g, 0.082 mmol), and the mixture was stirred for 4 days at 344
K to give a yellow solution. After removal of the solvent under
vacuum, the residue was extracted with dichloromethane/petroleum
ether (1/4) and the extracts chromatographed on an alumina column
at 288 K. Elution with dichloromethane/petroleum ether (1/1) gave a
yellow fraction yielding, after removal of solvents, compound cis-
CP
CP
CP
3
3
3
1
2
5
2, C (Cy)], 28.2 [d, J = 13, C (Cy)], 28.0 [d, J = 11, C (Cy)],
CP CP
4
1
5.8 [s, 2C (Cy)]. Data for isomer B: H NMR: δ 6.27, 6.21 (2s, 2 ×
H, Cp), 3.79 (d, J = 2, 3H, NMe), 2.80−0.60 (m, 22H, Cy).
PH
13
1
C{ H} NMR: δ 105.1, 102.9 [2s, Cp], 67.3 [s, NMe], 49.5 [d, J
=
CP
1
1
2
1
3
2
1
4, C (Cy)], 43.7 [d, J = 11, C (Cy)], 36.6 [d, J = 2, C (Cy)],
4.6 [d, JCP = 4, C (Cy)], 33.2 [d, J = 6, C (Cy)], 29.5 [s, C (Cy)],
8.1 [d, J = 17, 2C (Cy)], 27.3 [d, J = 11, C (Cy)], 27.1 [d, J =
4, C (Cy)], 25.8, 25.4 [2s, C (Cy)].
Preparation of [W Cp (μ-PCy )(μ-κ :η -MeNO)(NO) ]-
CF SO ) (4b). Neat CF SO Me (20 μL, 0.182 mmol) was added
CP CP
2
2
2
CP
3
3
[Mo
due to the presence of some residual excess P(OPh)
P(O)(OPh) . Further purification was achieved by the slow diffusion
Cp
(μ-PCy
){μ-NP(OPh)
}(NO)
3
] (cis-7) as an oily residue
2
CP
CP
CP
2
2
2
3
4
and
3
1
2
2
2
2
2
3
(
of layers of diethyl ether and petroleum ether into a concentrated
solution of the above product in toluene. This yielded yellow crystals
3
3
3
3
to a solution of compound 1b (0.015 g, 0.019 mmol) in
L
Inorg. Chem. XXXX, XXX, XXX−XXX