Inorganic Chemistry
Article
1
3
1
2
C{ H} NMR (62.9 MHz, C D ): δ 218.9 (d, J = 7.8 Hz, CO),
temperature. During this time, the color changed from red to yellow.
6
6
CP
3
2
1
(
46.3 (d, J = 3.7 Hz, o-C), 132.7 (d, J = 6.2 Hz, ipso-C), 130.2
d, J = 1.7 Hz, p-C), 126.4 (d, J = 3.3 Hz, NCH), 124.3 (d, J
PPh Cl (140 mg, 38 mmol) was added, and the suspension formed
4
CP
CP
5
2
4
was stirred for additional 20 h. The yellow precipitate was filtered off
and subsequently extracted with toluene (40 mL). Storage of the
yellow-orange extract at −24 °C for 24 h afforded 95 mg (0.11 mmol,
yield 43%) of a yellow, crystalline solid that was found to be
CP
CP
CP
=
1.0 Hz, m-C), 29.0 (s, CH), 24.7 (s, CH ), 23.0 (s, CH ). IR
3 3
−
1
(
solid): v
hexane): v
vis (MeCN, c = 4.0 ·10 M): λ [nm] (ε [l mol cm ]) 366
̃ [cm ] = 1981 (s), 1921 (s) vCO, 1698 (s) vNO. IR (n-
[cm ] = 2000 (m), 1951 (m) vCO, 1735 (m) vNO. UV−
−5 −1 −1
−
1
̃
1
1
spectroscopically pure. H NMR (250 MHz, C
D ): δ 9.32 (d, JPH =
max
max
6
6
2
86 Hz, 1 H, PH), 7.38−7.00 (m, 26 H, C H and C H ), 6.23 (d,
(
6600), 450 (sh). C H FeN O P (549.43): calcd C 61.21, H 6.60,
6
3
6
5
28
36
3
3
3
3
N 7.65; found C 61.35, H 6.65, N 7.59.
JPH = 5.5 Hz, 2 H, NCH), 4.21 (sept, JHH = 6.8 Hz, 2 H, CH), 3.79
(sept, JHH = 6.7 Hz, 2 H, CH), 1.70 (d, JHH = 6.8 Hz, 6 H, CH
1.53 (d, JHH = 6.7 Hz, 6 H, CH
1.36 (d, JHH = 6.7 Hz, 6 H, CH
Preparation of 4sat. The reaction of phosphenium salt 1 (0.56
g, 1.00 mmol) and ferrate 2 (0.71 g, 1.00 mmol) in thf (15 mL) and
the workup of the reaction mixture were carried out as described for
sat
3
3
),
),
): δ
3
3
3
), 1.48 (d, JHH = 6.8 Hz, 6 H, CH
). P NMR (101.2 MHz, C
3
3
3
31
D
6
3
6
1
13
1
. The product was obtained as an orange, crystalline solid (50 mg,
.09 mmol, yield 9%). Even if no satisfactory elemental analysis could
139.6 (d, JPH = 286 Hz), 22.3 (br). A satisfying C NMR spectrum
−
1
0
could not be obtained due to low solubility. IR (solid): v
1897 (s), 1820 (s) vCO; 1622 (s) vNO; 2066 (w) vPH.
(889.84): calcd C 70.19, H 6.46, N 4.72; found
̃ [cm ] =
1
be obtained, the product was found to be spectroscopically pure. H
3
NMR (400 MHz, C D ): δ 7.23−7.05 (m, 6 H, C H ), 3.50 (d, J
=
C H57FeN O P
52 3 3 2
6
6
6
3
PH
3
C 67.29, H 6.32, N 4.45. The low carbon content found in the
microanalysis is presumably due to carbide formation during the
combustion process. The spectroscopic data reveal no detectable
impurity.
4
.2 Hz, 4 H, NCH ), 3.38 (sept, J = 6.8 Hz, 4 H, CH), 1.42 (d,
2 HH
3
3
J
= 6.8 Hz, 12 H, CH ), 1.18 (d, J = 6.8 Hz, 12 H, CH ).
3 HH 3
HH
31
1
13
1
P{ H} NMR (161.9 MHz, C D ): δ 281.4 (s). C{ H} NMR
100.5 MHz, C D ): δ 221.3 (d, J = 7.8 Hz, CO), 149.9 (d, J
.9 Hz, o-C), 135.3 (d, J = 8.4 Hz, ipso-C), 131.8 (br, p-C), 126.2
br, m-C), 56.0 (d, JCP = 3.1 Hz, NCH ), 31.4 (s, CH), 27.5 (s,
6
2
6
3
(
2
=
6
6
CP
CP
2
Preparation of PPh
0.20 mmol) in Et O (10 mL) with MeLi (0.14 mL of a 1.6 M soln. in
Et O, 0.22 mmol) and PPh Cl (100 mg, 30 mmol) was carried out as
described for PPh [6]. Storage of the yellow-orange extract at −24 °C
for 24 h gave 85 mg (0.09 mmol, yield 47%) of an orange, crystalline
[8]. The reaction of a solution of 4 (110 mg,
4
CP
2
2
(
2
−1
2
4
CH ), 26.1 (s, CH ). IR (solid): v [cm ] = 1987 (s), 1974 (s), 1928
̃
(
3
3
−
1
4
s), 1916 (s) vCO; 1728 (s), 1698 (s) vNO. IR (thf): v
994 (m), 1940 (m) vCO; 1724 (m) vNO. UV−vis (MeCN, c = 1.9 ·
0
̃
[cm ] =
1
1
1
1
−
4
−1
−1
solid. H NMR (400 MHz, thf-d
8
): δ 9.83 (d, 1 H, JPH = 286 Hz,
M): λ [nm] (ε [l mol cm ]) 345 (2200), 420 (sh).
max max
PH), 7.94−7.66 (m, 20 H, C H and C H ), 7.27−7.06 (m, 6 H,
6
3
6
5
Preparation of 5. The reaction of phosphenium salt 1 (0.56 g,
3
3
C H and C H ), 5.87 (d, J = 4.7 Hz, 2 H, NCH), 3.97 (sept, J
6.6 Hz, 2 H, CH), 3.77 (sept, J = 6.7 Hz, 2 H, CH), 1.47 (s, 3
H, PCH ), 1.33 (d, J = 6.6 Hz, 6 H, CH ), 1.29 (d, J = 6.6 Hz,
6
3
6
5
PH
HH
1
.00 mmol) and chromate 3 (0.74 g, 1.00 mmol) in thf (15 mL) was
3
=
HH
carried out as described for 4. The residue obtained after removal of
the solvent under reduced pressure was extracted with n-hexane (40
mL). The resulting dispersion was filtered, and the filtrate was
concentrated to a volume of about 20 mL. Storage at −24 °C for 24 h
produced a deep-red, crystalline solid (270 mg, 0.47 mmol, yield
4
3
3
3
HH
3
HH
3
3
6
6
H, CH ), 1.24 (d, J = 6.6 Hz, 6 H, CH ), 1.10 (d, J = 6.6 Hz,
3 HH 3 HH
3
1
H, CH3). P NMR (161.9 MHz, thf-d ): δ 168.9 (s), 24.0 (br). A
satisfying C NMR spectrum could not be obtained due to low
̃ [cm ] = 1888 (s), 1810 (s) vCO; 1604 (s)
vNO. C H FeN O P (903.84): calcd C 70.43, H 6.58, N 4.65;
8
13
−1
solubility. IR (solid): v
1
7%). H NMR (250 MHz, C D ): δ 7.28−7.06 (m, 6 H, C H ), 6.18
d, J = 7.3 Hz, 2 H, NCH), 3.16 (sept, J = 6.9 Hz, 4 H, CH),
.32 (d, J = 6.9 Hz, 12 H, CH ), 1.11 (d, J = 6.9 Hz, 12 H,
HH 3 HH
6
6
6
3
3
3
53 59
3
3 2
(
1
PH HH
found C 70.04, H 6.61, N 4.64.
3
3
Reaction of 4 with NaN . A solution of 4 (110 mg, 0.20 mmol),
31
1
13
1
3
CH3). P{ H} NMR (101.2 MHz, C D ): δ 269.8 (s). C{ H}
6
6
NaN (13 mg, 0.20 mmol), and catalytic amounts of LiCl in thf was
2
3
NMR (62.9 MHz, C D ): δ 231.1 (d, J = 15.6 Hz, CO), 146.7 (d,
31
6
6
CP
stirred for 10 h at 60 °C. A P NMR spectrum of the reaction mixture
161.9 MHz, thf) showed the resonances of 2-azido diazaphospholene
3
2
5
JCP = 2.5 Hz, o-C), 132.5 (d, J = 6.0 Hz, ipso-C), 129.6 (d, J
=
CP
CP
(
9
2
4
1
.5 Hz, p-C), 124.9 (d, J = 1.8 Hz, NCH), 123.9 (d, J = 1.3 Hz,
27
31
28
CP
CP
(δ P = 119.0 ppm) and secondary diazaphospholene oxide 10
m-C), 28.1 (s, CH), 23.7 (s, CH ), 22.2 (s, CH ). IR (solid): v
[
hexane): v
C H CrN O P (573.59): calcd C 60.73, H 6.33, N 7.33; found C
6
̃
31
3
3
(δ P = 4.8 ppm), which were identified by comparison with
authentic samples. No attempt to workup was made.
−1
cm ] = 2016 (m), 1951 (m) 1931 (s) vCO; 1664 (s) vNO. IR (n-
−
1
̃ [cm ] = 2025 (m), 1968 (m) vCO; 1688 (m) vNO.
Reaction of PPh [6] with H(OEt ) [TRISPHAT]. PPh [6] (25
4
2 2
4
29
36
3
4
mg, 30 μmol) and H(OEt ) [TRISPHAT] (26 mg, 30 μmol) were
2 2
0.84, H 6.43, N 7.22.
dissolved in toluene (5 mL). The solution was stirred for 20 h at
ambient temperature. During this time, the color changed from yellow
to orange, and a colorless precipitate formed. Filtration and removal
of the solvent from the filtrate afforded an orange-red oil which was
Preparation of 5sat. The reaction of phosphenium salt 1sat (0.38
g, 0.68 mmol) and chromate 3 (0.60 g, 0.82 mmol) in thf (10 mL)
was carried out as described for 4. The residue obtained after removal
of the solvent under reduced pressure was extracted with n-hexane
31
31
characterized by P NMR spectroscopy. P NMR (161.9 MHz,
(
30 mL). The resulting dispersion was filtered, and the filtrate was
−
+
C D ): δ −80.0 (s, TRISPHAT ), 22.5 (br, PPh ), 239.1 (s, 4),
6
6
4
1
1
concentrated to a volume of about 15 mL. Storage at −24 °C for 24 h
produced 55 mg (0.10 mmol, yield 14%) of an orange-red, crystalline
solid. The product used for analytical characterization contained a
minor amount of hydrolysis product 10 which could not be separated
by fractional recrystallization due to similar solubilities. H NMR (250
MHz, C D ): δ 7.29−7.01 (m, 6 H, C H ), 3.42 (d, J = 3.5 Hz, 4
H, NCH), 3.33 (sept, J = 6.9 Hz, 4 H, CH), 1.35 (d, J = 6.9
Hz, 12 H, CH ), 1.18 (d, J = 6.9 Hz, 12 H, CH ). P{ H} NMR
(
δ 230.1 (d, J = 17.8 Hz, CO), 148.6 (d, J = 2.2 Hz, o-C), 134.3
(
1
26.9 (d, J = 307 Hz, unidentified), 137.6 (d, J = 346 Hz,
PH PH
unidentified).
Reaction of 4 with LiBEt H/Et NHCl. Excess LiBEt H (50 μL
sat
3
3
3
sat
of a 1 M solution in thf) was added to a solution of 4 (20 mg, 36
μmol) in Et O (0.4 mL) in an NMR tube. Formation of Li[6 ] was
verified by P NMR spectroscopy (δ P = 132.3 (d, J = 296 Hz)).
Solid Et NHCl was added. A P NMR spectrum indicated formation
1
sat
2
3
31
31
1
6
6
6
3
PH
PH
3
3
31
HH
HH
3
3
31
1
sat
31
3
HH
3
of a mixture with 4 as the main product. P NMR (101.2 MHz,
1
3
1
sat
1
101.2 MHz, C D ): δ 303.3 (s). C{ H} NMR (62.9 MHz, C D ):
Et O): δ 279.7 (s, 4 ), 136.6 (d, J = 348 Hz, unidentified), 122.4
6
6
6
6
2
P
H
2
3
1
1
CP
CP
(d, J = 303 Hz, unidentified), 8.4 (s, unidentified), 5.0 (d, J
PH
=
PH
2
5
4
d, J = 8.1 Hz, ipso-C), 129.7 (d, J = 1.5 Hz, p-C), 124.9 (d, J
607 Hz, 10).
CP
CP
CP
2
=
1.2 Hz, m-C), 53.9 (d, J = 2.0 Hz, NCH ), 28.9 (s, CH), 25.0 (s,
3
Reaction of 5 with LiBEt H and Et NHCl. A 1 M solution of
CP
2
3 3
−
1
CH ), 23.7 (s, CH ). IR (solid): v
̃
[cm ] = 2023 (m), 1958 (m)
LiBEt H in thf (0.13 mL, 0.13 mmol) was added to a solution of 5
3
3
−
1
1
(
929 (s) vCO; 1656 (s) vNO. IR (thf): v
m) vCO, 1678 (m) vNO. C H CrN O P (575.61): calcd C 60.51,
̃
[cm ] = 2029 (w), 1966
(50 mg, 90 μmol) in Et O (5 mL). The mixture was stirred for 1 h at
2
2
9
36
3
4
ambient temperature, and the solvent was removed under reduced
3
1
H 6.65, N 7.30; found C 62.75, H 7.57, N 6.79.
pressure. Formation of Li[7] was verified by NMR spectroscopy ( P
1
1
31
Preparation of PPh [6]. A 1 M solution of LiHBEt in thf (0.28
NMR (101.2 MHz, C D ): δ = 155.6 (d, J = 301 Hz); H, P
4
3
6 6 PH
1
mL, 0.28 mmol) was added to a solution of 4 (140 mg, 0.25 mmol) in
HMQC (250 MHz, C D ): δ = 9.58 (d, J = 301 Hz, PH)). For the
6 6 PH
Et O (10 mL). The mixture was stirred for 20 h at ambient
2
reaction with Et NHCl, a new ethereal solution of Li[7] was prepared
3
C
Inorg. Chem. XXXX, XXX, XXX−XXX