Diphosphanylketenimines
3872±3878
1
2
.80 ppm (s,3H; CH
3
); 31P{ H} NMR (121.5 MHz,CD
2
Cl
2
): d À0.50 (d,
remaining oil was washed with hexane (3 Â 10 mL) affording a yellow solid.
2
2
31
1
J(P,P) 85 Hz), À84.10 ppm (d, J(P,P) 85 Hz); IR (Nujol): nÄ 1718
This was recrystallized from CH
2
Cl
2
/hexane. Yield 75%. P{ H} NMR
À1
2
2
(
(
CO),1586 cm
(CN); elemental analysis calcd (%) for C40
H
33NO
4
P
2
(121.5 MHz,CDCl
3
): d 28.90 (d, J(P,P) 24 Hz),4.96 ppm (d, J(P,P)
1
3
1
653.6): C 73.50,H 5.09,N 2.14; found: C 72.43,H 4.82,N 1.91.
24 Hz);
C
NMR (75.5 MHz,CD
2
Cl
2
): d 170.51 (dd, J(P,C) 94,
3
2
2
3
1
1
J(P,C) 12 Hz; CO),147.10 (dd,
J(P,C) 14, J(P,C) 7 Hz; CN),
Compound 6: P{ H} NMR (121.5 MHz,CD
2
Cl
2
): d 28.50 (ddd,
4
4
2
3
3
148.07 (d, J(P,C) 4 Hz; C NC),136.02 (d,
J(P,C) 4 Hz; C
2
NC),
J(P1,P2) 52,
J(P1,P3) 24,
J(P1,P4) 6 Hz; P1), À22.83 (d,
1
1
2
3
2
41,44 ppm (dd, J(P,C) 131 Hz, J(P,C) 97 Hz; PCP); IR (KBr): nÄ
J(P1,P2) 52 Hz; P2),14.32 (dd, J(P1,P3) 24, J(P3,P4) 4 Hz; P3),
À1
.85 ppm (dd, 3J(P1,P4) 6, 2J(P3,P4) 4 Hz; P4); for the numbering of
1634 (CO),1587 cm
(CN); elemental analysis calcd (%) for
6
39 30 2 2 2
C H N O P (620.6): C 75.48,H 4.87,N 4.51; found: C 75.76,H 4.65,N
phosphorus atoms see Scheme 3.
4
.53.
Compound 7: Hydrogen peroxide (18 mL of a 30% aqueous solution,
.16 mmol) was added to a solution of 6 (0.16 g,0.16 mmol) in CH
50 mL). A slight darkening of the orange color of the solution was
observed. Evaporation of the solvent to dryness under vacuum gave an oily
residue,which was converted to an orange solid by washing with hexane.
Compound 14: A mixture of compound 8 (50 mg,0.1 mmol) and ethyl
isothiocyanate (87 mL,1 mmol) was heated in refluxing toluene (20 mL) for
0
(
2 2
Cl
3
h. The solvent was evaporated to dryness and the remaining residue
washed with hexane affording an orange solid which was recrystallized
1
3
1
1
2
from CH
2
Cl
2
/Hexane. Yield 70%. H NMR (300 MHz,CDCl
3
): d 6.7 ± 7.7
Yield: 90%. P{ H} NMR (121.5 MHz,CD
2
Cl
2
): d 29.96 (td, J(P1,P2)
3
3
3
3
2
(23H; Ph),6.40 (d, J(H,H) 6 Hz,2H; ortho-NPh),4.30 (q, J(H,H)
3
1, J(P1,P3) 12, J(P1,P4) 6 Hz; P1),29.40 (dd,
J(P1,P2) 31,
3
31
1
5
3
2
5
6 Hz,2H; CH
(121.5 MHz,CDCl
2
N),1.20 ppm (t, J(H,H) 6 Hz,3H; CH
3
); P{ H} NMR
J(P2,P3) 6 Hz; P2),13.71 (dt, J(P1,P3) 12, J(P3,P4) 6, J(P2,P3)
2
2
3
2
3
): d 25.02 (d, J(P,P) 25 Hz),20.50 ppm (d, J(P,P)
6
Hz; P3),7.33 ppm (t,
J(P1,P4) 6, J(P3,P4) 6 Hz; P4); for the
1
3
1
2
5 Hz);
C
NMR (75.5 MHz,CD
2
Cl
2
): d 192.18 (dd, J(P,C) 74,
numbering of phosphorus atoms see Scheme 3; elemental analysis calcd
3
2
2
J(P,C) 8 Hz; CS),151.60 (dd,
J(P,C) 16, J(P,C) 10 Hz; CN),
(
%) for C64
N 2.90.
Compound 9: Hydrogen peroxide (18 mL of a 30% aqueous solution,
.16 mmol) was added to a solution of 6 (80 mg,0.08 mmol) in CH Cl
30 mL). The solution instantly changed from orange to dark red.
50 2 4
H N OP (987.0): C 77.88,H 5.10,N 2.83; found: C 77.25,H 4.98,
3
1
1
1
47.67 (s; CNC),41.84 (d, J(P,C) 5 Hz; CH
2
),4 07 ,2 (dd,
J(P,C)
1
24 Hz, J(P,C) 87 Hz; PCP),12.30 ppm (s; CH
3
); IR(KBr): nÄ 1631
À1
(
(
CN),1262 cm (CS); elemental analysis calcd (%) for C35
30 2 2
H N OP S
0
(
2
2
588.6): C 71.42,H 5.14,N 4.76; found: C 71.72,H 4.82,N 4.52.
Compound 15: A mixture of compound 8 (50 mg,0.1 mmol) and N-
methylpropargylamine (17 mL,0.2 mmol) was heated in refluxing toluene
(20 mL) for 10 min. Then the solution was concentrated to 5 mL under
vacuum. Addition of hexane (10 mL) resulted in the formation of a white
Evaporation of the solvent to dryness under vacuum gave an oily residue,
which was converted to a red solid by washing with hexane. Yield: 90%.
P{ H} NMR (121.5 MHz,CD
3
1
1
2
2
Cl
2
): d 36.01 (td, J(P1,P2) 31,
3
3
2
J(P1,P3) 31, J(P1,P4) 21 Hz; P1),29.22 (d, J(P1,P2) 31 Hz; P2),
3
2
3
solid. Yield 70%. Crystals of 15 suitable for X-ray analysis were obtained
1
2
9.26 (dd, J(P1,P3) 31, J(P3,P4) 8 Hz; P3),0.45 ppm (dd, J(P1,P4)
1, 2J(P3,P4) 8 Hz; P4); for the numbering of phosphorus atoms see
1
by recrystallization from CH
2
Cl
2
/hexane. H NMR (300 MHz,CDCl
3
): d
),1.65 ppm (d,
); P{ H} NMR (121.5 MHz,CDCl
): d 36.22
3
6
.75 (d, J(P,H) 29 Hz,1H; C CH),2.81 (s,3H; NCH
3
Scheme 3; elemental analysis calcd (%) for C64
H 5.02,N 2.79; found: C 76.42,H 4.91,N 2.85.
50 2 2 4
H N O P (1003.0): C 76.64,
3
31
1
J(P,H) 12 Hz,3H; CCH
3
3
2
2
13
(
d, J(P,P) 27 Hz),9.27 ppm (d, J(P,P) 27 Hz); C NMR (75.5 MHz,
2 2
Compound 8: A solution of 9 (80 mg,0.08 mmol) in toluene (20 mL) was
heated at the refluxing temperature for 10 min. Over this period it turned
colorless. The solvent was evaporated to dryness affording a white solid,
CD
2
Cl
2
): d 150.10 (dd, J(P,C) 12, J(P,C) 5 Hz; CN),147.47 (d,
1 1
4
J(P,C) 5 Hz; CNC),86.32 (dd, J(P,C) 82 Hz, J(P,C) 7 Hz; PCP),
2
4
2.87 (s; NCH
3
),15.20 ppm (d, J(P,C) 6 Hz; CCCH
3
); elemental analysis
1
which was recrystallized from hexane. Yield 90%. H NMR (300 MHz,
calcd (%) for C36
H 5.68,N 5.23.
32 2 2
H N OP (570.6): C 75.78,H 5.65,N 4.91; found: C 75.56,
3
3
CDCl
3
): d 7.78 (dd, J(P,H) 11, J(H,H) 7 Hz,4H; ortho-PPh),6.5 ±
31 1
7
.5 ppm (21H; Ph); P{ H} NMR (121.5 MHz,CDCl
3
): d 27.53 (d,
X-ray crystallographic study: Data collection was carried out on an Enraf ±
Nonius KappaCCD diffractometer for 5a, 13 and 15. Graphite-monochro-
2
2
13
J(P,P) 87 Hz; PO), À14.80 ppm (d, J(P,P) 87 Hz);
C
NMR
2
2
(
75.5 MHz,CD
2
Cl
2
1
): d 168.33 (dd, J(P,C) 10, J(P,C) 3 Hz; P
2
CC
mated CuKa radiation (l 1.54184 ä)
a
was used. The structures were
1
N),52.58 ppm (dd, J(P,C) 105, J(P,C) 50 Hz; P
2
CCN); IR (CH
2 2
Cl ):
solved by direct methods,and refined by full-matrix least-squares methods
À1
nÄ 2018 cm (CCN); elemental analysis calcd (%) for C32
1 2
H25NO P
with the following program packages: DIRDIF92[ and SHELXL-97
22]
[23]
.
(
501.5): C 76.64,H 5.02,N 2.79; found: C 76.55,H 5.01,N 2.65.
Compound 12a: Dimethyl acetylenedicarboxylate (21 mL,0.17 mmol) was
added to a solution of 8 (80 mg,0.16 mmol) in CH Cl (20 mL). After the
mixture had been stirred for 5 min,the solvent was evaporated to dryness
under vacuum to afford an oily residue. This was dissolved in CH Cl
5 mL) and hexane (20 mL) was added to obtain a violet solid,which was
Relevant crystallographic data and details of the refinement for the three
structures are given in Table 1. CCDC-180291 (5a),CCDC-180292 ( 13),
2
2
Table 1. Crystallographic data for compounds 5a, 13,and 15.
2
2
(
5
a
13
15
1
recrystallized from CH
CDCl
2
Cl
2
/hexane. Yield 85%. H NMR (300 MHz,
3
3
3
): d 7.85 (dd, J(P,H) 14, J(H,H) 7 Hz,4H; ortho-PPh),6.8 ±
formula
formula weight
temperature [K]
crystal system
space group
a [ä]
b [ä]
c [ä]
a [8]
C
769.69
200
monoclinic
P2 /n
12.2664(13)
18.4425(12)
18.0416(9)
90
44
H
37NO
8
P
2
C
620.59
200
monoclinic
P2 /c
16.5595(10)
8.5353(4)
22.3717(14)
90
39
H
30
N
2
O
2
P
2
36 32 2 2
C H N OP
570.58
200
3
7.7 (19H,Ph),6.55 (d,
J(H,H) 7 Hz,2H; ortho-CNPh),3.10 (s,3H;
3
1
1
CH
(
CD
3
2
),3.50 ppm (s,3H; CH
3
); P{ H} NMR (121.5 MHz,CDCl
3
): d 31.60
2
13
d, J(P,P) 34 Hz),29.20 ppm (d, J(P,P) 34 Hz); C NMR (75.5 MHz,
monoclinic
P2 /c
2
3
2
Cl
2
): d 164.83 (d, J(P,C) 17 Hz; CO),161.81 (d, J(P,C) 4 Hz;
1
1
1
4
CO),150.58 (d, J(P,C) 4 Hz; CNC),53.14 (s; CH
3
),52.58 (s; CH
),
13.0516(8)
15.1368(10)
16.3258(9)
90
3
1
1
3
(
C
1.08 ppm (dd, J(P,C) 169, J(P,C) 24 Hz; PCP); IR (Nujol): nÄ 1751
À1
CO),1733 (C O),1579 cm
(CN); elemental analysis calcd (%) for
38
H
31NO
5
P
2
(643.6): C 70.91,H 4.85,N 2.18; found: C 70.63,H 4.79,N
2
.16.
b [8]
g [8]
V [ä ]
Z
106.1850(10) 91.383(3)
112.330(4)
90
2983.4(3)
4
1.270
1.564
3.66 ± 69.77
9725
5546
90
90
Compound 12b: This compound was prepared similarly to 12a by treating
8
in CH
3
3919.7(5)
4
3160.2(3)
4
(50 mg,0.1 mmol) with methyl acetylenecarboxylate (11 mL,0.12 mmol)
1
2
Cl
2
for 1 h. Yield 85%. H NMR (300 MHz,CDCl
3
): d 6.7 ± 8.2
À3
2
4
1
calcd [gcm
]
1.304
1.464
3.50 ± 68.17
6232
1.304
1.549
2.67 ± 63.65
4208
(
25H; Ph),6.63 (dd,
J(P,H) 19 Hz, J(P,H) 3 Hz, 1H; C CH),
À1
); 3 P{ H} NMR (121.5 MHz,C
1 1
m[mm
q range [8]
reflections collected
independent reflections
goodness-of-fit on F
final R indices [I > 2s(I)]; R1, wR2 0.0709,0.1806 0.0629,0.1299 0.0590,0.1390
R indices (all data); R1, wR2 0.1098,0.2447 0.1346,0.1636 0.1008,0.1694
]
3
.09 ppm (s,3H; CH
3
6
D
6
): d 29.76 (d,
2
2
J(P,P) 38 Hz),28.40 ppm (d, J(P,P) 38 Hz); IR(Nujol): nÄ 1733 (C
À1
O),1554 cm
(CN); elemental analysis calcd (%) for C36
3 2
H29NO P
6232
4208
(
585.6): C 73.84,H 4.99,N 2.39; found: C 73.37,H 4.75,N 2.19.
Compound 13: A mixture of compound 8 (80 mg,0.16 mmol) and phenyl
isocyanate (87 mL,0.80 mmol) was heated in refluxing toluene (20 mL) for
0 min. The solvent was then evaporated to dryness under vacuum and the
2
1.048
0.931
1.077
1
Chem. Eur. J. 2002, 8,No. 17
¹ 2002 WILEY-VCH Verlag GmbH & Co. KGaA,Weinheim
0947-6539/02/0817-3877 $ 20.00+.50/0
3877