A Novel Approach to 1,2,4-Thiadiphospholes and 1,2-Thiaphospholes
FULL PAPER
(C6D6): δ ϭ 1.41 [s, 3 H, CH3], 1.50 [d, 3JH,P ϭ 1.2 Hz, 3 H, CH3],
1.22Ϫ1.64 [m, 12 H, CH2], 1.75Ϫ1.83 [m, 2 H, CH2], 1.86Ϫ1.94
(5 mL) was added, and the mixture was stirred for 24 h at room
temperature. After removal of all volatile materials, the residue, in
[m, 2 H, CH2], 2.22Ϫ2.33 [m, 4 H, CH2]. 13C{1H} NMR (C6D6): the case of 7a, was placed in a sublimation apparatus. Excess hexa-
δ ϭ 23.1 [d, 4JC,P ϭ 2.2 Hz, CH2], 23.2 [s, CH2], 26.2 [s, CH2], 26.4 carbonylchromium was removed at 40 °C/2.4·10Ϫ2 mbar, and the
[s, CH2], 33.2 [br s, CH3], 33.8 [br s, CH3], 42.1 [d, 3JC,P ϭ 11.3 Hz,
product sublimed at 85Ϫ105 °C/2.4·10Ϫ2 mbar. For the corres-
ponding tungsten complex 7b, the residue was subjected to column
3
3
CH2], 43.1 [dd, JC,P ϭ 13.7, JC,P ϭ 10.4 Hz, CH2], 44.8 [pt,
2JC,P ϭ 2JC,P ϭ 16.5 Hz, Cq], 45.7 [dd, 2JC,P ϭ 14.9, 3JC,P ϭ 5.6 Hz, chromatographic workup with n-pentane as eluent.
1
1
Cq], 209.4 [d, JC,P ϭ 68.3 Hz, C(5)], 221.9 [dd, JC,P ϭ 77.9,
Pentacarbonyl[2-η1-(3,5-di-tert-butyl-1,2,4-thiadiphosphole)]-
chromium(0) (7a): This compound was synthesized by use of hexa-
carbonylchromium(0) (71 mg, 0.32 mmol) and 1,2,4-thiadiphos-
phole 3a (44 mg, 0.19 mmol). Yield: 41 mg (51%); yellow solid; m.p.
1JC,P ϭ 71.9 Hz, C(3)]. 31P{1H} NMR (C6D6): δ ϭ 254.4 [d, 2JP,P ϭ
2
49.3 Hz, P(4)], 267.0 [d, JP,P ϭ 49.3 Hz, P(2)]. MS (EI, 70 eV):
m/z (%) ϭ 312 (85) [Mϩ], 297 (18) [Mϩ Ϫ CH3], 279 (24) [Mϩ
Ϫ
SH], 249 (9) [P(CMecHex)2ϩ], 172 (17) [SPCMecHexϩ] 109 (35)
[CMecHexϩ], 97 (92) [MecHexϩ]. HRMS: m/z: calcd. for
C16H26P2S 312.1231; found 312.1231.
1
4
127 °C (dec.). H NMR (C6D6): δ ϭ 1.29 [d, JH,P ϭ 1.2 Hz, 9 H,
C(CH3)3], 1.50 [s, 9 H, C(CH3)3]. 13C{1H} NMR (C6D6): δ ϭ 34.1
[dd, 3JC,P ϭ 11.2, 4JC,P ϭ 1.6 Hz, C(CH3)3], 35.8 [dd, 3JC,P ϭ 10.8,
3JC,P ϭ 10.0 Hz, C(CH3)3], 41.0 [dd, 2JC,P ϭ 19.7, 2JC,P ϭ 11.7 Hz,
3,5-Bis(1-methylcyclopent-1-yl)-1,2,4-thiadiphosphole (3c): This
compound was synthesized by use of S8 (359 mg, 11.2 mmol), tri-
chlorothiotantalum(V) (2, 320 mg, 1.00 mmol), toluene (25 mL),
(1-methylcyclopent-1-yl)phosphaacetylene (1c, 2.40 mL, 1920 mg,
10.2 mmol), triphenylphosphane (3.33 g, 12.8 mmol), and n-pent-
2
3
C(CH3)3], 42.1 [dd, JC,P ϭ 16.7, JC,P ϭ 2.6 Hz, C(CH3)3], 204.4
1
2
2
[dd, JC,P ϭ 63.4, JC,P ϭ 8.0 Hz, C(5)], 214.8 [d, JC,P ϭ 13.3 Hz,
1
1
COax], 215.1 [dd, JC,P ϭ 75.3, JC,P ϭ 33.1 Hz, C(3)], 221.1 [d,
2JC,P ϭ 2.4 Hz, COeq]. 31P{1H} NMR (C6D6): δ ϭ 264.7 [d, 2JP,P ϭ
1
ane (50 mL). Yield: 900 mg (62%); colorless oil. H NMR (C6D6):
2
56.1 Hz, P(2) or P(4)], 266.0 [d, JP,P ϭ 56.1 Hz, P(2) or P(4)]. IR
3
δ ϭ 1.45 [s, 3 H, CH3], 1.50 [d, JH,P ϭ 1.2 Hz, 3 H, CH3],
(KBr): ν˜ ϭ 2965 (CH), 2072 (CO), 1993 (CO), 1980 (CO), 1929
1.55Ϫ1.73 [m, 8 H, CH2], 1.81Ϫ1.88 [m, 2 H, CH2], 1.91Ϫ1.98 [m,
(CO). MS (EI, 70 eV): m/z (%) ϭ 424 (17) [Mϩ], 368 (15) [Mϩ
Ϫ
2 H, CH2], 2.20Ϫ2.30 [m, 4 H, CH2]. 13C{1H} NMR (C6D6): δ ϭ
2 CO], 312 (32) [Mϩ Ϫ 4 CO], 284 (95) [Mϩ Ϫ 5 CO], 169 (43)
[P(CtBu)2ϩ], 131 (33) [P2CtBuϩ], 69 (64) [CtBuϩ], 57 (100) [tBuϩ].
C15H18CrO5P2S (424.31): calcd. C 42.46, H 4.28; found C 42.84,
H 4.23.
4
4
24.3 [pt, JC,P
ϭ
4JC,P ϭ 1.4 Hz, CH2], 24.5 [d, JC,P ϭ 1.2 Hz,
CH2], 32.5 [dd, 3JC,P ϭ 8.6, 4JC,P ϭ 1.4 Hz, CH3], 33.8 [dd, 3JC,P ϭ
9.8, 3JC,P ϭ 8.6 Hz, CH3], 44.4 [d, 3JC,P ϭ 10.8 Hz, CH2], 44.8 [dd,
3JC,P ϭ 13.3, JC,P ϭ 8.8 Hz, CH2], 52.1 [dd, JC,P ϭ 18.7, JC,P
ϭ
3
2
2
17.8 Hz, Cq], 53.1 [dd, 2JC,P ϭ 16.1, 3JC,P ϭ 5.6 Hz, Cq], 209.4 [dd,
Pentacarbonyl[2-η1-(3,5-di-tert-butyl-1,2,4-thiadiphosphole)]-
tungsten(0) (7b): This compound was synthesized by use of hexa-
carbonyltungsten(0) (370 mg, 1.05 mmol) and 1,2,4-thiadiphos-
1JC,P ϭ 65.1, 2JC,P ϭ 4.4 Hz, C(5)], 220.2 [dd, 1JC,P ϭ 76.9, 1JC,P ϭ
69.3 Hz, C(3)]. 31P{1H} NMR (C6D6): δ ϭ 253.5 [d, JP,P
ϭ
2
2
51.3 Hz, P(4)], 265.6 [d, JP,P ϭ 51.3 Hz, P(2)]. MS (EI, 70 eV):
phole 3a (109 mg, 0.47 mmol). Yield: 56 mg (22%); yellow solid.
m/z (%) ϭ 284 (100) [Mϩ], 269 (13) [Mϩ Ϫ CH3], 251 (36) [Mϩ
Ϫ
4
1H NMR (C6D6): δ ϭ 1.29 [s, 9 H, C(CH3)3], 1.52 [d, JH,P
ϭ
SH], 221 (55) [P(CMecPen)2ϩ], 95 (53) [CMecPenϩ], 83 (20)
[MecPenϩ]. HRMS: m/z: calcd. for C14H22P2S 284.0918; found
284.0918.
1.1 Hz, 9 H, C(CH3)3]. 13C{1H} NMR (C6D6): δ ϭ 34.1 [dd,
4
3
3
3JC,P ϭ 11.2, JC,P ϭ 1.6 Hz, C(CH3)3], 35.8 [pt, JC,P ϭ JC,P
ϭ
2
2
10.8 Hz, C(CH3)3], 40.9 [dd, JC,P ϭ 19.3, JC,P ϭ 10.4 Hz,
2
3
C(CH3)3], 42.1 [dd, JC,P ϭ 16.9, JC,P ϭ 2.8 Hz, C(CH3)3], 195.2
3,5-Bis(1,1-dimethylpropyl)-1,2,4-thiadiphosphole (3d): This com-
pound was synthesized by use of S8 (121 mg, 3.50 mmol), trichloro-
thiotantalum(V) (2, 1725 mg, 5.40 mmol), toluene (5 mL), tert-pen-
tylphosphaacetylene (1d, 1.76 in hexamethyldisiloxane, 1.71 mL,
3.00 mmol), triphenylphosphane (2.52 g, 9.60 mmol), and n-pent-
[d, 2JC,P ϭ 8.0, 1JC,W ϭ 126.1 Hz, COeq], 198.6 [d, 2JC,P ϭ 34.5 Hz,
1
2
COax], 205.0 [dd, JC,P ϭ 66.3, JC,P ϭ 10.8 Hz, C(5)], 207.4 [dd,
1JC,P ϭ 77.1, JC,P ϭ 23.3 Hz, C(3)]. 31P{1H} NMR (C6D6): δ ϭ
1
2
1
2
208.2 [d, JP,P ϭ 61.0, JP,W ϭ 247.4 Hz, P(2)], 259.8 [d, JP,P
ϭ
61.0 Hz, P(4)]. MS (EI, 70 eV): m/z (%) ϭ 556 (23) [Mϩ], 500 (19)
[Mϩ Ϫ 2 CO], 444 (17) [Mϩ Ϫ 4 CO], 416 (46) [Mϩ Ϫ 5 CO], 232
(31) [Mϩ Ϫ W(CO)5], 169 (15) [P(CtBu)2ϩ], 131 (12) [P2CtBuϩ],
69 (38) [CtBuϩ], 57 (100) [tBuϩ]. C15H18O5P2SW (556.16).
1
ane (20 mL). Yield: 112 mg (29%); colorless oil. H NMR (C6D6):
δ ϭ 0.74 [t, 3JH,H ϭ 7.4 Hz, 3 H, CH2CH3], 0.79 [t, 3JH,H ϭ 7.5 Hz,
4
3 H, CH2CH3], 1.48 [d, JH,P ϭ 1.6 Hz, 6 H, C(CH3)2], 1.53 [dd,
4JH,P ϭ 2.4, 4JH,P ϭ 0.8 Hz, 6 H, C(CH3)2], 1.77 [q, 3JH,H ϭ 7.5 Hz,
3
2 H, CH2CH3], 1.88 [q, JH,H ϭ 7.4 Hz, 2 H, CH2CH3]. 13C{1H}
Tricarbonyl[η5-(3,5-di-tert-butyl-1,2,4-thiadiphosphole)]-
molybdenum(0) (9a): In a pressure Schlenk tube, the molybdenum
complex 8a (344 mg, 1.14 mmol) was suspended in THF (7 mL)
and the heterocyclic compound 3a (103 mg, 0.44 mmol) was added.
The mixture was then stirred for 16 h at 65 °C, during which the
color changed to deep red. After removal of all volatile materials,
the residue was dissolved in a small amount of n-pentane and fil-
tered through Celite. After concentration of the solution under va-
cuum, the material was transferred to a sublimation apparatus for
purification. A white impurity was obtained first at 45 °C/1.6·10Ϫ2
mbar, followed by the product 9a at 75Ϫ85 °C/1.6·10Ϫ2 mbar.
NMR (C6D6): δ ϭ 9.4 [d, 4JC,P ϭ 1.7 Hz, CH2CH3], 9.5 [pt, 4JC,P ϭ
3
4JC,P ϭ 1.3 Hz, CH2CH3], 32.3 [d, JC,P ϭ 12.7 Hz, C(CH3)2], 33.0
3
3
3
[dd, JC,P ϭ 15.7, JC,P ϭ 8.9 Hz, C(CH3)2], 39.9 [dd, JC,P ϭ 6.4,
4JC,P ϭ 1.3 Hz, CH2CH3], 40.9 [dd, JC,P ϭ 8.7, JC,P ϭ 7.4 Hz,
3
3
2
2
CH2CH3], 44.5 [dd, JC,P ϭ 17.8, JC,P ϭ 17.0 Hz, C(CH3)2], 45.3
[dd, 2JC,P ϭ 15.5, 3JC,P ϭ 5.7 Hz, C(CH3)2], 208.1 [dd, 1JC,P ϭ 66.6,
2JC,P ϭ 4.2 Hz, C(5)], 219.3 [dd, JC,P ϭ 78.4, JC,P ϭ 70.4 Hz,
1
1
C(3)]. 31P{1H} NMR (C6D6): δ ϭ 258.0 [d, JP,P ϭ 49.0 Hz, P(4)],
2
2
269.5 [d, JP,P ϭ 49.0 Hz, P(2)]. MS (EI, 70 eV): m/z (%) ϭ 260
(32) [Mϩ], 245 (3) [Mϩ Ϫ CH3], 231 (100) [Mϩ Ϫ CH2CH3], 145
(4) [P2CtPenϩ], 71 (22) [tPenϩ]. HRMS: m/z: calcd. for C12H22P2S
260.0918; found 260.0917.
1
Yield: 59 mg (33%); red oil. H NMR (C6D6): δ ϭ 1.06Ϫ1.10 [m,
2
C(CH3)3]. 31P{1H} NMR (C6D6): δ ϭ 53.3 [d, JP,P ϭ 33.1 Hz,
General Procedure for the Synthesis of the η1 Complexes 7: In an
irradiation apparatus, the required amount of the hexacarbonylme-
tal was dissolved in THF (50 mL), and the solution was irradiated
P(4)], 83.1 [d, JP,P ϭ 33.1 Hz, P(2)]. MS (EI, 70 eV): m/z (%) ϭ
2
414 (38) [Mϩ], 386 (20) [Mϩ Ϫ CO], 358 (13) [Mϩ Ϫ 2 CO], 330
(100) [Mϩ Ϫ 3 CO], 232 (32) [Mϩ Ϫ Mo(CO)3], 169 (10)
with water cooling for about 25 min (HPK 125 W Philips). After [P(CtBu)2ϩ], 69 (8) [CtBuϩ], 57 (18) [tBuϩ]. C13H18MoO3P2S
cessation of CO evolution, the 1,2,4-thiadiphosphole 3a in THF
(412.23).
Eur. J. Org. Chem. 2002, 1664Ϫ1676
1671