iPr P(S)NHP(O)(OPh) , 3. Method A. Reagents:
Ph P(S)NHP(S)iPr , 9. Method B. Reagents: Ph P(S)NH
2
2
2
2
2
2
(PhO) P(O)NH (3.60 g, 0.014 mol), NaH (1.00 g, 0.042 mol),
(3.40 g, 0.015 mol), NaH (1.10 g, 0.046 mol), iPr P(S)Cl (2.70 g,
2
2
2
iPr P(S)Cl (2.60 g, 0.014 mol) in THF (60 ml); 2 M HCl (75
0.015 mol) in DMF (80 ml); 2 M HCl (75 ml) used for proto-
2
ml) used for protonation and CH Cl (50 ml ] 3) used for
nation and CH Cl (50 ml ] 3) used for extraction. Yield:
2
2
2 2
extraction. Yield: (1.30 g, 22.6%); mp: 129È130 ¡C; micro-
(3.00 g, 54.0%); mp: 104È105 ¡C; microanalysis: found C
analysis: found C 54.37, H 6.28, N 3.28, S 7.91%; calc. for
56.70, H 6.72, N 3.72, S 16.25%; calc. for C H NP S : C
18 25 2 2
C
H
NO P S: C 54.40, H 6.34, N 3.52, S 8.07%; selected
56.67, H 6.61, N 3.67, S 16.81%; selected IR data: 2611w
[l(NH)], 918s [l(PNP)], 781m, 627m, 614w [l(PS)] cm~1; 1H
NMR: d(NÈH) 3.8.
18 25
3 2
IR data: 2749m [l(NH)], 1195s [l(PO)], 1162m, 958s
[l(PNP)], 775m, 765m, 616w [l(PS)] cm~1; 1H NMR:
d(NÈH) 5.7.
PhC(O)NHP(S)(OPh) , 10. Method A. Reagents:
2
iPr P(Se)NHP(O)(OPh) , 4. Method A. Reagents:
(PhO) P(S)NH (2.00 g, 0.008 mol), NaH (0.55 g, 0.023 mol),
2
2
2
2
2
(PhO) P(O)NH (3.70 g, 0.015 mol), NaH (1.08 g, 0.045 mol),
PhC(O)Cl (1.10 g, 0.008 mol) in THF (50 ml); 50 ml 2 M HCl
2
iPr P(Se)Cl (3.50 g, 0.015 mol) in THF (100 ml); 2 M HCl (75
used for protonation and 3 ] 30 ml CH Cl used for extrac-
2
2 2
ml) used for protonation and CH Cl (50 ml ] 3) used for
tion. Yield: (0.70 g. 25.1%); mp: 124È125 ¡C; microanalysis:
2
2
extraction. Yield: (2.25 g, 34.1%); mp: 99È101 ¡C; micro-
found C 61.88, H 4.26, N 3.75, S 8.51%; calc. for
analysis: found
C
48.72,
H
5.45,
N
2.80%; calc. for
C
H
NO PS: C 61.78, H 4.37, N 3.79, S 8.68%; selected IR
19 16
3
C
H
NO P Se: C 48.66, H 5.67, N 3.15%; selected IR
data: 3221m [l(NH)], 1664s [l(CO)], 1161m, 641m, 616w
18 25
3 2
data: 2750m [l(NH)], 1194s [l(PO)], 1162m, 956s [l(PNP)],
774m, 767m, 589m, 572m [l(PSe)] cm~1; 1H NMR: d(NÈH)
[l(PS)] cm~1; 31P-M1HN NMR: d 55.4 (s); 1H NMR: d(NÈH)
2.2.
6.2.
Synthesis of palladium complexes
Ph P(Se)NHP(S)(OPh) , 5. Method A. Reagents:
To a stirred suspension of the ligand in methanol, potassium
tert-butoxide was added. After stirring to obtain a homoge-
2
2
Ph P(Se)NH (2.70 g, 0.010 mol), NaH (0.70 g, 0.029 mol),
2
2
(PhO) P(S)Cl (2.74 g, 0.010 mol) in THF (50 ml); 2 M HCl (50
nous mixture, Pd(OAc) dissolved in methanol was added
2
2
ml) used for protonation and CH Cl (30 ml ] 3) used for
extraction. Yield: (0.65 g, 12.8%); mp: 130È132 ¡C; micro-
dropwise. The mixture was stirred for 6 to 12 h. The resulting
2
2
red precipitate was collected by Ðltration, washed with meth-
anol and dried in vacuo.
analysis: found C 54.62, H 3.98, N 2.70, S 6.22%; calc. for
C
H
NO P SSe: C 54.55, H 4.01, N 2.65, S 6.07%; selected
24 21
2 2
IR data: 3124m, 2600w [l(NH)], 1157m, 947s [l(PNP)],
776m, 653m [l(PS)], 547w [l(PSe)] cm~1; 1H NMR: d(NÈH)
[Ph P(S)NP(O)(OPh) ] Pd, 11. Reagents: 1 (0.233 g, 0.500
2
2 2
mmol) in MeOH (30 ml); Pd(OAc) (0.056 g, 0.250 mmol) in
2
3.6.
MeOH (20 ml); KOtBu (0.056 g, 0.500 mmol). Yield: (0.210 g,
81.1%); mp: 197 ¡C; microanalysis: found: C 55.71, H 3.84, N
Ph P(S)NHP(S)(OPh) , 6. Method A. Reagents:
2.55, S 5.72%; calc. for C
H
N O P PdS : C 55.69, H 3.89,
2
2
48 40
2
6 4
2
Ph P(S)NH (3.00 g, 0.013 mol), NaH (0.93 g, 0.039 mol),
N 2.71, S 6.19%; selected IR data: 1226m [l(PNP)], 1192s
[l(PO)], 1158s, 566m, 541w [l(PS)] cm~1; 31P-M1HN NMR: d
[2.2 (d) and 87.3 (d) 2J(PÈP) 11.6 Hz; d 3.0 (d) and 40.3 (d)
2J(PÈP) 18.9 Hz.
2
2
(PhO) P(S)Cl (3.66 g, 0.013 mol) in THF (50 ml); 2 M HCl (50
2
ml) used for protonation and CH Cl (30 ml ] 3) used for
2
2
extraction. Yield: (1.60 g, 25.8%); mp: 128È129 ¡C; micro-
analysis: found C 60.01, H 4.43, N 2.75, S 13.14%; calc. for
C
H
NO P S : C 59.87, H 4.40, N 2.91, S 13.32%; selected
[iPr P(S)NP(O)(OPh) ] Pd, 12. Reagents: 3 (0.200 g, 0.503
24 21
2 2 2
2
2 2
IR data: 3126m, 2600w [l(NH)], 1157s, 935s [l(PNP)], 776m,
767m, 627m, 614w [l(PS)] cm~1; 1H NMR: d(NÈH) 5.2.
Method B. Reagents: Ph P(S)NH (3.00 g, 0.013 mol), NaH
(0.93 g, 0.039 mol), (PhO) P(S)Cl (3.66 g, 0.013 mol) in DMF
(70 ml); 2 M HCl (50 ml) used for protonation and CH Cl
(30 ml ] 3) used for extraction. Yield: (3.95 g, 63.8%); mp:
128È129 ¡C; microanalysis: found C 59.84, H 4.38, N 3.02, S
13.25%; calc. for C
13.32%; selected IR data: 3126m, 2600w, 1157s, 935s, 776m,
mmol) in MeOH (15 ml); Pd(OAc) (0.056 g, 0.250 mmol) in
2
MeOH (20 ml); KOtBu (0.056 g, 0.503 mmol). Yield: (0.067 g,
29.6%); mp: 164.5È165 ¡C; microanalysis: found C 47.98, H
2
2
5.51, N 3.25, S 8.23%; calc. for C
H
N O P PdS : C 48.09,
2
36 48
2
6 4
2
H 5.38, N 3.12, S 7.13%; selected IR data: 1238s [l(PNP)],
1191s [l(PO)], 1161s, 578s, 572s [l(PS)] cm~1; 31P-M1HN
NMR: d [ 0.5 (d) and 125.0 (d) 2J(PÈP) 18.0 Hz.
2
2
H
NO P S : C 59.87, H 4.40, N 2.91, S
24 21
2 2 2
[Ph P(S)NP(S)(OPh) ] Pd, 13. Reagents: 6 (0.250 g, 0.519
2
2 2
766m, 627m, 614w cm~1; 1H NMR: d(NÈH) 5.2.
mmol) in MeOH (15 ml); Pd(OAc) (0.058 g, 0.258 mmol) in
2
MeOH (20 ml); KOtBu (0.058 g, 0.519 mmol). Yield: (0.210 g.
75.8%); mp: 196È198 ¡C; microanalysis: found C 54.07, H
iPr P(S)NHP(S)(OPh) , 7. Method B. Reagents:
2
2
(PhO) P(S)NH (3.90 g, 0.015 mol), NaH (1.10 g, 0.046 mol),
3.63, N 2.47, S 13.15%; calc. for C
H
N O P PdS : C
2
2
48 40
2
4 4
4
iPr P(S)Cl (2.70 g, 0.015 mol) in DMF (80 ml); 2 M HCl (100
54.01, H 3.78, N 2.62, S 12.01%; selected IR data: 1221m
[l(PNP)], 1161s, 562m, 548m [l(PS)] cm~1; 31P-M1HN NMR:
d 42.3 (d) and 46.8 (d) 2J(PÈP) 27.3 Hz.
2
ml) used for protonation and CH Cl (50 ml ] 3) used for
2
2
extraction. Yield: (4.40 g, 72.4%); mp: 86È87 ¡C; microanaly-
sis: found C 52.34, H 6.23, N 3.24, S 15.78%; calc. for
C
H
NO P S : C 52.29, H 6.09, N 3.39, S 15.51%; selected
Acknowledgements
18 25
2 2 2
IR data: 2668m [l(NH)], 1161s, 923s [l(PNP)], 769m, 762m,
626m, 610m [l(PS)] cm~1; 1H NMR: d(NÈH) 4.8.
This work was supported by the Grant Agency of the Czech
Republic (grant no. 203/99/0067) and by the Ministry of Edu-
cation of the Czech Republic (MSM 143100011). We also
thank Prof. Steinar Husebye, Department of Chemistry, Uni-
versity of Bergen, Norway, for very valuable discussions.
Ph P(O)NHP(S)(OPh) , 8. Method B. Reagents:
2
2
(PhO) P(S)NH (3.00 g, 0.011 mol), NaH (0.80 g, 0.033 mol),
Ph P(O)Cl (2.68 g, 0.011 mol) in DMF (50 ml); 2 M HCl (50
ml) used for protonation and the precipitate was collected by
2
2
2
Ðltration. Yield: (4.30 g, 81.7%); mp: 194È197 ¡C; microanaly-
sis: found C 62.03, H 4.54, N 2.97, S 6.45%; calc. for
References
1
A. Schmidpeter, R. Bohm and H. Groeger, Angew. Chem., Int. Ed.
Engl., 1964, 3, 704.
C
H
NO P S: C 61.93, H 4.55, N 3.01, S 6.89%; selected
24 21
3 2
IR data: 2629s [l(NH)], 1182s [l(PO)], 1162s, 955s, 937s
[l(PNP)], 779s, 620w [l(PS)] cm~1; 1H NMR: d(NÈH) 8.5.
2
O. Navratil, E. Herrmann and P. Slezak, Coll. Czech. Chem.
Commun., 1987, 52, 1708.
1262
New J. Chem., 2001, 25, 1256È1263