A 2,2′-Biphosphinine Dianion
Organometallics, Vol. 18, No. 17, 1999 3351
and K. With Li, the surface of the metal may need to be
activated by stripping with a spatula. The color slowly evolved
from yellow to deep purple and then to dark green, indicating
the end of the reaction (2 h in general). Dianions 3a -c are
highly oxygen sensitive and P NMR samples were prepared
using a glovebox. Solutions of 3a -c can be kept at room
temperature for days without apparent decomposition. A
Ta ble 1. Cr ysta llogr a p h ic Da ta a n d Exp er im en ta l
P a r a m eter s for th e Str u ctu r e of 6
mol formula
mol wt
C24H30P2Ru
481.49
3
1
cryst descripn (habit/size (mm))
dark red needles/
0.10 × 0.12 × 0.16
monoclinic
C2/c
19.2260(5)
20.2100(5)
12.2910(2)
111.0550(13)
4456.91(18)
8
cryst syst
space group
a (Å)
b (Å)
c (Å)
solution of 3a in THF-d
8
was sealed in a NMR tube in order
to measure all NMR spectra.
3
1
1
3
a : P NMR (C
4
D
8
4 8
O, 255 K) δ -13.90; H NMR (C D O,
2
55 K) δ 1.90 (s, 6H, 2 × Me), 1.93 (s, 6H, 2 × Me), 6.69 (pt,
â (deg)
2
AA′XX′, 2H, J (H-P) ) 38.50 Hz, H6,6′), 7.01 (s, AA′XX′, H3,3′);
3
V (Å )
1
3
C NMR (C
4
D
8
O, 255 K) δ 23.5 (s, Me), 24.40 (s, Me), 116.35
Z
3
(bs, AXX′, C2,2′ or C4,4′ or C5,5′), 116.80 (bs, AXX′, C2,2′ or C4,4′ or
d (g/cm )
1.435
C
C
3
5,5′), 122.30 (bs, AXX′, C3,3′), 124.05 (bs, AXX′, C2,2′ or C4,4′ or
F(000)
1984
0.853
150.0(1)
26.36
0-24; 0-25; -15 to +14
9386
4558
µ (cm-1)
3
1
5,5′), 140.75 (bs, AXX′, C6,6′). 3b: P NMR (C
4
H
8
O) δ -6.10.
c: 3 P NMR (C
1
T (K)
max θ (deg)
hkl ranges
4 8
H O) δ -4.20.
0
Gen er a l P r oced u r e for th e P r ep a r a tion of [M (d p p e)-
(
4
4,4′,5,5′-tetr a m eth yl-2′,2′-bip h osp h in in e)] (4a , M ) Ni;
b, M ) P d ; 4c, M ) P t). The complexes [M(dppe)Cl ] (0.1
no. of rflns measd
no. of indep rflns
no. of rflns used
refinement type
hydrogen atoms
no. of params refined
rfln/param ratio
wR2
2
mmol) were added at -80 °C to a solution of dianion 3a in
THF prepared as previously described. After 5 min of stirring
at -80 °C, the resulting mixture was slowly warmed to room
temperature and then stirred for 30 min. After evaporation of
THF, dry toluene (10 mL) was added and the solution obtained
was filtered through a pad of Celite under a nitrogen atmo-
sphere. After evaporation of toluene, complexes 4a -c were
recovered as moisture- and oxygen-sensitive red-orange pow-
ders. Yield: 80%. The compounds 4b,c were too sensitive to
give satisfactory elementary analyses. For characterizations
of 4a , see ref 13.
3869
2
F ; full matrix
mixed
251
15
0.0923
0.0297
I > 2σ(I)
1.12
R1
criterion
GOF
diff peak/hole (e Å-3)
0.46 (0.13)/-0.60 (0.13)
1
in a 3:1 ratio. Washing with hexanes (2 × 5 mL) gave pure
4
b: 31P NMR (C
6
D
6
) δ 176.60 (t, 2J (P-P) ) 23.2 Hz,
complex 5. Yield: 44 mg (80%). For characterizations, see ref
1
C
14
H
16
P
2
), 38.5 (t, dppe); H NMR (C
6
D
6
) δ 1.55-2.24 (m, 4H,
2e.
CH
Me), 6.99-7.07 (m, 12H, C
), 8.64 (pt, AA′XX′, 2H, J (H-P) )
2
), 2.24 (s, 6H, 2 × Me), 2.27 (d, J (H-P) ) 2.15 Hz, 6H, 2
Syn th esis of (η
p h osp h in in e)r u th en iu m (0) 6. The dimer [Ru(η
(30.6 mg, 0.05 mmol) was added to a solution of dianion 3a
(49 mg, 2 mmol), prepared as described above in THF, at -80
°C. The resulting red solution was kept at this temperature
with stirring for 10 min and then slowly warmed to room
6
-Cym en e)(4,4′,5,5′-tetr a m eth yl-2′,2′-bi-
-C H14)Cl2]2
×
6
H
5
), 7.65-7.75 (m, 10H, CH of
6
1
0
2
C
6
H
5
and H3,3′ of C14
H
16
16
P
2
1
3
9
2
.80 Hz, H6,6′ of C14
H
P
2
); C NMR (C
4.65 (s, Me), 29.95 (ptt, AXX′Y , ∑J (C-P) ) 42.73 Hz, J (C-
), 129.00-129.90 (CH of C masked
), 130.45 (ptt, AXX′Y , ∑J (C-P) ) 18.30 Hz, J (C-P)
) 131.65 (s, CH of C ), 133.95 (d,
J (C-P) ) 16.85 Hz, CH of C ), 139.00 (m, AXX′Y
6 6
D ) δ 23.25 (s, Me),
3
2
P) ) 5.00 Hz, 2 × CH
by C
)
2
6 5
H
4
31
6
D
6
2
temperature. After 20 min of stirring, a P NMR control
3.05 Hz, C3,3′ of C14
H
16
P
2
6
H
5
indicated that the reaction was complete. The solvent was then
evaporated, and 40 mL of dry toluene was added. The resulting
red mixture was stirred for an additional 20 min and then
filtered under a nitrogen atmosphere. After evaporation of
toluene, complex 6 was recovered as a red powder which is
not particularly air-sensitive and can be weighed in air.
Further purification can be achieved by crystallizing 6 in
hexanes or pentane at room temperature. Yield: 37 mg (80%).
6
H
5
2
, C6,6′ of
C
C
C
14
14
14
H
H
H
16
16
16
P
P
P
2
2
2
), 141.55 (AXX′, ∑J (C-P) ) 13.74 Hz, C4,4′ or C5,5′ of
), 142.60 (AXX′, ∑J (C-P) ) 12.20 Hz, C4,4′ or C5,5′ of
), 155.50 (m, AXX′Y
2
, C2,2′ of C14
H
16
P
2
).
2
1
4
c: 31P NMR (C
6
D
6
) δ 152.45 (t, J (P-P) ) 63.80 Hz, J (P-
1
95
1
195
Pt) ) 3045.00 Hz, C14
H
16
P
2
), 43.40 (t, J (P- Pt) ) 3799.95
) δ 1.54-2.24 (m, 4H, CH ), 2.27 (s,
H, 2 × Me), 2.35 (d, J (H-P) ) 2.15 Hz, 6H, 2 × Me), 7.01-
.05 (m, 12H, C ), 7.61-7.9 (m, 10H, CH of C ), 8.43-
.58 (m, 2H, H3,3′ of C14 ), 8.82 (pt, AA′XX′, 2H, J (H-P)
13.50 Hz, H6,6′ of C14
5.25 (pt, Me), 30.90 (ps, 2 × CH
masked by C ), 133.80 (s, CH of C
J (C-P) ) 14.95 Hz, C3,3′ of C14
), 139.15 (m, C4,4′ or C5,5′ of C14
1
Hz, dppe); H NMR (C
6
D
6
2
3
1
1
6
7
8
)
2
P NMR (C D ): δ 200.5. H NMR (C D ): δ 1.13 (d, 6H,
6
6
6
6
3
6
H
5
6
H
5
2
J (H-H) ) 6.87 Hz, Me of isopropyl), 2.06 (s, 3H, Me of C H14),
2.29 (s, 6H, Me of C H P ), 2.41 (s, 6H, Me of C H P ), 2.48
14 16 2 14 16 2
(septuplet, 1H, J (H-H) ) 6.87 Hz, CH of isopropyl), 5.36 (m,
4H, CH of C H14), 8.02 (AA′XX′, 2H, ∑J (H-P) ) 25.63 Hz,
1
0
H
16
P
2
1
3
3
H
16
P
2
); C NMR (C
6
D
6
) δ 23.30 (s, Me),
2
), 129.00-130.1 (CH of C H
6 5
1
0
6
D
6
6
H
5
), 134.00 (pt, AXX′,
), 137.00 (m, C6,6′ of
), 143.80 (pt, AXX′,
), 148.75 (m,
H3,3′ or H6,6′), 8.46 (AA′XX′, 2H, ∑J (H-P) ) 20.49 Hz, H3,3′ or
13
∑
C
∑
H
16
P
H
2
H6,6′). C NMR (C D ): δ 21.40 (s, Me of C H14), 22.50 (s, Me
6
6
10
14
H
16
P
2
16
P
2
of isopropyl), 24.30 (d, J (C-P) ) 2.70 Hz, Me of C H P ),
24.60 (t, J (C-P) ) 4.70 Hz, Me of C H P ), 33.00 (s, CH of
isopropyl), 80.60 (t, J (C-P) ) 2.40 Hz, CH of C H14), 82.80
2 2
1
4
16
2
J (C-P) ) 12.60 Hz, C4,4′ or C5,5′ of C14
, C2,2′ of C14 ).
H
16
P
2
1
4
16
2
2
AXX′Y
2
H
16
P
2
1
0
Syn th esis of Bis(4,4′,5,5′-tetr a m eth yl-2′,2′-bip h osp h in -
in e)n ick el(0) (5). Biphosphinine 1 (24 mg, 0.1 mmol) was
added at -80 °C to a THF solution of dianion 3a (24 mg, 0.1
mmol) prepared as previously described. The color of the
mixture rapidly changed from dark green to deep purple. After
(t, J (C-P) ) 2.40 Hz, CH of C10
14), 107.90 (t, 2J (C-P) ) 2.50 Hz, Cipso of
14), 129.00 (t, AXX′, ∑J (C-P) ) 14.70 Hz, C or C ), 130.00
or C masked by C ), 134.05 (t, AXX′, ∑J (C-P) ) 8.40
Hz, C ), 142.05 (t, AXX′, ∑J (C-P) ) 81.20 Hz, C2,2′), 142.25 (t,
AXX′, ∑J (C-P) 11.40 Hz, 6,6′). Anal. Calcd for
: C, 59.87; H, 6.28. Found: C, 59.60; H, 6.10.
Syn th esis of Tr is(4,4′,5,5′-tetr a m eth yl-2,2′-bip h osp h in -
in e)tu n gsten (0) 7. WCl (27 mg, 0.67 mmol) was added to a
H14), 95.05 (t, J (C-P) ) 2.50
Hz, Cipso of C10
H
C
10
H
4
5
(C
4
5
6 6
D
3
5
min of stirring, the resulting mixture was warmed to room
temperature and then stirred for an additional 10 min. The
reaction with [NiBr ‚DME] (31 mg, 0.1 mmol) was carried out
)
C
RuC24
30 2
H P
2
at -80 °C. The solution turned immediately dark red. After 5
min of stirring, the reaction mixture was warmed to room
temperature. The solvent was evaporated, and complex 5 was
6
solution of 3a (0.05 g, 0.2 mmol) at -80 °C in THF (5 mL).
The reaction mixture was stirred at this temperature for 10
min and then slowly warmed to room temperature. After 20
min of stirring, the solvent was evaporated and complex 7 was
3
1
extracted with dichloromethane (2 × 5 mL). P NMR showed
two resonances corresponding to complex 5 and biphosphinine