1
,2- and 1,3-Diphosphanes Containing Four Chiral Rhenium Fragments
FULL PAPER
1
5
NO), 830 (s, PF). H NMR (400 MHz, CDCl
7
H, CH Cl ), 5.19 (s, 10 H, C ), 5.15 (s, 10 H, C HЈ ), CH
2
3
): PPh
3
at δ = 7.41–
{(η -C
P)(ON)Re(η -C
at charged with (SRe
5
H
5
)Re(NO)(PPh
3
)(CH
)} (n = 0/1, 11/12): (A) A Schlenk tube was
Re)-7·(CH Cl (0.120 g, 0.0431 mmol)
2 2 2 2 n 2 2
)} {POCH (CH ) CH PO}{(CH )-
1
5
.20 (m, 60 H); 6.08 [dm, J(H,P) = 460 Hz, 2 H, PH], 5.32 (s, 4 (Ph
3
5 5 2
H
2
2
5
H
5
5
5
2
S S
Re Re
S
2
2 2
)
1
3
1
.15–1.91 (m, 8 H), 1.52–1.38 (m, 6 H). C{ H} NMR and THF (10 mL). Then tBuOK (1.0 m in THF; 0.134 mL,
1
(100.5 MHz, CD
3
NO
2
): δ = PPh
3
at 135.1 [d, J(C,P) = 46 Hz, i],
0.13 mmol) was added dropwise with stirring. After 30 min, the
1
2
1
34.5 [d, J(C,P) = 47 Hz, iЈ], 134.0 [d, J(C,P) = 10 Hz, o], 139 [d, solvent was removed by oil pump vacuum. The remaining workup
2
4
4
J(C,P) = 11 Hz, oЈ], 131.3 [d, J(C,P) = 2 Hz, p], 131.2 [d, J(C,P) was conducted in air. The residue was extracted with CH
2
Cl
2 Hz, pЈ], 129.4 [d, J(C,P) = 10 Hz, m], 129.2 [d, J(C,P) = (20 mL), and the extract filtered through Celite (2×2 cm). The fil-
0 Hz, mЈ]; 91.4 (s, C ), 91.1 (s, CЈ ), 53.8 (s, CH Cl ), 28.9 trate was concentrated to ca. 5 mL and layered with ether (10 mL).
d, J(C,P) = 14 Hz, PCH C], After 2 days, the supernatant was decanted from a yellow powder,
C], 28.5 [d, 2J(C,P) = 9 Hz, CCH
], –32.6 [d, J(C,P) = 39 Hz, which was dried by oil pump vacuum to give (SRe Re)-11
]. P{ H} NMR (161.8 MHz, CD NO ): δ = 72.1 (0.0963 g, 0.0409 mmol, 95 %). M. p. 195–198 °C (dec).
], 23.3 [d, J(P,P) = 14 Hz, Re (2352.5): calcd. C 50.04, H 3.94, N 2.38; found
C 49.81, H 3.63, N 2.09. IR (thin film [cm ]): ν˜ = 1637 (s, NO),
2
3
3
=
1
5
H
5
5
H
5
2
2
1
[
2
2
1
1
–
27.3 [d, J(C,P) = 21 Hz, ReCH
2
Re Re
S S S
3
1
1
ReCЈH
2
3
2
3
3
[
apparent t, J(P,P) = 16 Hz, PCH
2
C
98
H
92
N
4
O
6
P
6
4
3
1
–1
3 3
PPh ], 22.6 [d, J(P,P) = 18 Hz, PЈPh ], –142.3 [sept, J(P,F) =
+
1
7
18 Hz]. MS (FAB, 3-NBA): m/z (%) = 2337 (2) [M – H] , 558
1181 (m, PO). H NMR (400 MHz, [D
7.22 (m, 60 H); 5.45 (br. s, 10 H, C ), 5.29 (br. s, 10 H, C
CH at 3.12 (br. s, 2 H), 2.64 (m, 2 H), 2.46 (m, 2 H), 2.24 (m, 4
3
H), 2.05 (m, 2 H). C{ H} NMR (100.5 MHz, [D at
8
]THF): PPh
3
at δ = 7.53–
5
+
(
100) [(η -C
5
H
5
)Re(NO)(PPh
)(CH
)} (n = 0/1, 9/10): (A) A glass vial was
Re)-7·(CH Cl (0.180 g, 0.0647 mmol)
and THF (5 mL) in a glove box. Then tBuOK (1.0 m in THF;
.142 mL, 0.14 mmol) was added dropwise with stirring, and the
vial sealed with a screw cap. After 30 min, the solvent was removed
by oil pump vacuum. [D ]Toluene (2 mL) was added with stirring.
After 10 min, the sample was passed through a PTFE syringe filter.
3
)(CH
2
)] .
5
H
5
5
5
HЈ ),
5
2
{
(
(η -C
Ph
5
H
5
)Re(NO)(PPh
3
2
)}
2
{PCH
2 2 n 2 2
(CH ) CH P}{(CH )-
1
3
1
5
8
]THF): PPh
δ = 134.8 [d, J(C,P) = 53 Hz, i], 134.4 [d, J(C,P) = 11 Hz, o],
3
P)(ON)Re(η -C
5
H
5
2
1
2
charged with (SRe
S
Re
Re
S S
2
2 2
)
3
1
32.1 (s, p), 131.7 (s, pЈ), 129.8 [d, J(C,P) = 11 Hz, m], 129.6 [d,
3
1
J(C,P) = 9 Hz, mЈ]; 92.4 (s, C
5
1
H
5
), 91.0 (s, CЈ
C], –18.3 [d, J(C,P) = 22 Hz, ReCH
5
H
5
), 28.7 [d, J(C,P)
], –22.8 [d,
]THF
): δ = 88.2 or 80.5 [apparent t, J(P,P) = 17 Hz, or br. s,
0
=
56 Hz, PCH
2
2
1
31
1
J(C,P) = 39 Hz, ReCЈH
or CDCl
PO], 25.6 or 28.3 [d, J(P,P) = 16 Hz, or br. s, PPh
2 8
]. P{ H} NMR (161.8 MHz, [D
8
3
3
3
1
13
3
], 21.2 or 26.4
3
[d, J(P,P) = 18 Hz, or br. s, PЈPh ]. MS (FAB, 3-NBA): m/z (%) =
An aliquot of the orange filtrate was assayed by NMR ( H, C,
3
31
P). The aliquot was readded and the solvent removed by oil pump
vacuum to give (SRe Re)-9 as an orange powder (0.138 g,
.0595 mmol, 92 %). M. p. 178–180 °C (dec). C98 Re
2320.5): calcd. C 50.73, H 4.00, N 2.41; found C 51.12, H 3.88, N
+
+
5
2
5 5
353 (5) [M] , 2337 (4) [M – O] , 558 (100) [(η -C H )Re-
Re Re
S S S
+
3 2
(NO)(PPh )(CH )] .
0
(
H
92
N
4
O
4
P
6
4
(
B) A Schlenk flask was charged with (SRe
Re Re
S S SRe)-7 (0.131 g,
–1
1
2
.25. IR (thin film [cm ]): ν˜ = 1610 (s, NO). H NMR (400 MHz,
]toluene): PPh at δ = 7.61–7.49 (m, 24 H), 6.93–6.91 (m, 36
H); 5.14 (s, 10 H, C ), 5.09 (s, 10 H, C HЈ ), CH at 2.60–2.50
m, 8 H), 1.73–1.56 (m, 4 H). C{ H} NMR (75.5 MHz, [D ]tolu-
at δ = 138.5 (d, J(C,P) = 50 Hz, i), 134.5 (d, J(C,P) =
0
0
1
.0501 mmol) and THF (10 mL). Then tBuOK (1.0 m in THF;
.16 mL, 0.16 mmol) was added dropwise with stirring. After
0 min, PhIO (0.034 g, 0.16 mmol)[ was added. The mixture
[D
8
3
5
H
5
5
5
2
39]
13
1
(
8
turned orange. After 2.5 h, the solvent was removed by rotary evap-
oration. The residue was extracted with benzene (6×5 mL). The
extracts were filtered through Celite (2×4 cm). The orange filtrate
was concentrated by rotary evaporation to ca. 2 mL, and hexanes
1
2
ene): PPh
3
2
3
1
0 Hz, o), 134.3 (d, J(C,P) = 10 Hz, oЈ), 129.8 (d, J(C,P) = 10 Hz,
m), 128.5 (s, p), 128.4 (s, pЈ); 91.7 (s, C ), 91.6 (s, CЈ ), 31.8
C], –8.1 (m, ReCH ), –11.8
). P{ H} NMR (121.5 MHz, [D ]toluene or [D
), 27.9 or 27.6 (br. s, PPh
5
H
5
5 5
H
[dd, J(C,P) = 14, J(C,P) = 7 Hz, PCH
2
2
(
80 mL) were added with vigorous stirring. The yellow-orange pre-
cipitate was collected by filtration, washed with hexanes (5 mL),
and dried by oil pump vacuum to give (SRe Re)-11 (0.085 g,
.036 mmol, 72 %). M. p. 200–203 °C (dec). C98 Re
4
3
1
1
(
m, ReCЈH
2
8
8
]
3
),
THF): δ = 37.5 or 34.9 (br. s, PCH
7.4 or 27.4 (br. s, PЈPh ).
2
Re Re
S S S
2
3
0
H
92
N
4
O
6
P
6
(
B) Complex (RRe
R
Re
R
Re
R
Re)-8·(CH
2
Cl
2
)
2
(0.150 g, 0.0536 mmol),
(2352.5): calcd. C 50.04, H 3.94, N 2.38; found C 50.41, H 4.23, N
2.08.
THF (10 mL) and tBuOK (1.0 m in THF; 0.161 mL, 0.16 mmol)
were combined in a procedure analogous to A. The toluene filtrate
was concentrated to ca. 3 mL and layered with pentane (10 mL).
After 3 days, the supernatant was decanted from an orange powder,
Re Re
(C) Complex (SReS S SRe)-8 (0.131 g, 0.0499 mmol), THF
(10 mL), tBuOK (1.0 m in THF; 0.16 mL, 0.16 mmol), and PhIO
(0.034 g, 0.16 mmol)[ were combined in a procedure analogous
to B. A similar workup (precipitation with 50 mL of hexanes; wash-
39]
which was dried by oil pump vacuum to give (RRe
0.078 g, 0.033 mmol, 62%). M. p. 164–166 °C (dec). C99
Re (2334.5): calcd. C 50.93, H 4.06, N 2.40; found C 50.29, H
.35, N 2.03. IR (thin film [cm ]): ν˜ = 1617 (s, NO). H NMR
400 MHz, C or [D ]toluene): PPh at δ = 7.74–7.70 or 7.64–
.61 (m, 10 H), 7.56–7.51 or 7.47–7.40 (m, 12 H), 7.11–7.08 or NMR (500 MHz, CDCl
.04–7.02 (m, 12 H), 7.03–6.95 or 6.97–6.89 (m, 26 H); 5.15 or 5.04 (s, 10 H, C ), 5.09 (s, 10 H, C
), 4.92 or 4.84 (s, 10 H, C HЈ ), CH at 2.69–2.61 or 1.48, 1.11 (6 m, 12 H). C{ H} NMR (125.7 MHz, CDCl
.57–2.52 (m, 6 H), 1.98–1.69 or 1.80–1.72 (m, 8 H). C{ H} at δ = 136.5 [d, J(C,P) = 51 Hz, i], 136.1 [d, J(C,P) = 52 Hz, iЈ],
Re Re
R R RRe)-10
(
P
4
(
7
7
(
H
94
N
4
O
4
-
6
4
ing with 2 mL) gave (SRe
S
Re
S
Re
S
Re)-12 (0.074 g, 0.0031 mmol,
PO. M. p. 190–192 °C
–1
1
62%) that typically contained ca. 5% of Ph
3
–
1
1
6
D
6
8
3
(dec). IR (thin film [cm ]): ν˜ = 1629 (s, NO), 1183 (w, PO). H
): PPh at δ = 7.69–7.06 (m, 60 H); 5.17
HЈ ), CH at 2.18, 2.08, 1.78, 1.63,
): PPh
3
3
3
5
H
5
5
5
2
1
3
1
s, 10 H, C
5
H
5
5
5
2
3
1
3
1
1
1
2
1
2
2
NMR (100.5 MHz, C
i], 137.4 (d, J(C,P) = 50 Hz, iЈ), 134.4 (d, J(C,P) = 10 Hz, o),
6
D
6
): PPh
3
at δ = 138.0 [d, J(C,P) = 50 Hz, 133.7 [d, J(C,P) = 12 Hz, o], 133.6 [d, J(C,P) = 10 Hz, oЈ], 129.9
1
2
3
3
(s, p), 128.3 [d, J(C,P) = 9 Hz, m], 128.3 [d, J(C,P) = 9 Hz, mЈ];
2
1
1
34.2 (d, J(C,P) = 11 Hz, oЈ), 129.8 (s, p), 131.1 (s, pЈ), 129.7 [d, 90.6 (s, C
5
2
H
5
), 90.5 (s, CЈ C],
34.7 [d, J(C,P) = 13 Hz, CCH C], –13.0 [d, J(C,P) = 57 Hz,
5
H
5
), 35.2 [d, J(C,P) = 12 Hz, PCH
2
3
3
1
J(C,P) = 10 Hz, m], 129.3 [d, J(C,P) = 10 Hz, mЈ]; 91.5 (s, C
5
H
5
),
C], ]. P{ H} NMR
3
C], –5.6 [dd, J(C,P) = 41, J(C,P) (202.4 MHz, CDCl ): δ = 78.8 [apparent t, J(P,P) = 13 Hz, PO],
2
1
3
1
31
1
9
2
1.1 (s, CЈ
4.6 [t, J(C,P) = 13 Hz, CCH
5
H
5
), 39.7 [dd, J(C,P) = 22, J(C,P) = 8 Hz, PCH
2
ReCH
2
], –13.5 [d, J(C,P) = 72 Hz, ReCЈH
2
2
1
2
3
2
1
2
3
3
=
5 Hz, ReCH
2
], –12.9 [dd, J(C,P) = 32, J(C,P) = 5 Hz, ReCЈH
P{ H} NMR (161.8 MHz, C ): δ = 31.4 (s, PCH ), 27.3 (s, MS (FAB, 3-NBA): m/z (%) = 2367 (9) [M] , 544 (100) [(η -C
PPh ), 26.8 (s, PЈPh ).
2
]. 26.7 [d, J(P,P) = 15 Hz, PPh
3
], 26.5 [d, J(P,P) = 13 Hz, PЈPh
3
].
)-
3
1
1
+
5
6
D
6
2
5 5
H
+
3
3
3
Re(NO)(PPh )] .
Eur. J. Inorg. Chem. 2005, 2983–2998
www.eurjic.org
© 2005 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
2995