4518 Organometallics, Vol. 22, No. 22, 2003
Owen et al.
thaw prior to use. 1H, 31P, and 13C NMR spectra were recorded
on a J EOL-EX270 spectrometer (270.17, 109.38, and 67.94
MHz, respectively) with TMS, H3PO4, and TMS, respectively,
as internal references. IR spectra were recorded on Research
C6H3(CH3)2 + 4 × PC6H5 + HN(C6H5)). MS (FAB+; m/z
(relative intensity): 769 (100) [M - BF4]+, 650 (15) [M - BF4
- {N(Ph)NHCdO)}]+, 504(26) [(dppe)Pd]+.
Series FT-IR using KBr disks in the range 4000-500 cm-1
.
Syn th esis of [P d {C(dCH2)N(Xy)C(dS)NHP h }(d p p e)]-
[BF 4] (6). Phenyl isothiocyanate (28.7 µL, 0.24 mmol) was
added to a stirring solution of Pd{C(Me)dNXy}(Cl)(dppe) (0.15
g, 0.22 mmol) in CH2Cl2 (25 mL). AgBF4 (0.04 g, 0.22 mmol)
was added as a solid. AgCl immediately precipitated from the
yellow solution, and within 5 min the solution turned pale
yellow. The reaction mixture was stirred for a further 10 min,
after which time the AgCl was filtered off. A pale yellow solid
(characterized as 6) was obtained by the reduction of the
solvent to 10 mL followed by addition of hexane (15 mL).
Yield: 0.13 g; 0.15 mmol; 68%. Anal. Found: C, 57.11; H, 4.63;
N, 2.92. Calcd for C43H41N2P2SBF4Pd‚0.5CH2Cl2: C, 57.02; H,
4.62; N, 3.06. IR (ν (KBr)): 3448 (N-H), 3054 (alkene C-H),
1592 m, 1534 s (CdC), 1359 (CdS), 1102, 1053 (BF4). 31P{1H}
Elemental analyses were carried out at the London Metro-
politan University. The complexes Pd(Me)(Cl)(COD),17 Pd(Me)-
(Cl)(P-P) (P-P ) dppp and dppe),18 Pd{C(Me)dNXy}(Cl)-
(dppe),9 Pd{C(Me)dNXy}(Cl)(dppp),9 and Pd(Ph)(I)(PPh3)2
19
were synthesized according to previously reported procedures.
Syn th esis of [P d {C(dCH2)N(Xy)C(dO)NHEt}(d p p e)]-
[BF 4] (3). Ethyl isocyanate (13.9 µL, 0.18 mmol) was added
to a stirring solution of Pd{C(Me)dNXy}(Cl)(dppe) (0.11 g, 0.16
mmol) in CH2Cl2 (20 mL). AgBF4 (0.03 g, 0.17 mmol) was
added as a solid to the reaction mixture. AgCl immediately
precipitated from the yellow solution. The reaction mixture
was stirred for a further 10 min, after which time the AgCl
was filtered off. A yellow solid (characterized as 3) was
obtained by concentrating the mixture under reduced pressure
(to approximately 10 mL) followed by addition of hexane (10
mL). Yield: 0.08 g; 0.10 mmol; 90%. Anal. Found: C, 55.73;
H, 5.00; N, 3.17. Calcd for C39H41N2P2OBF4Pd‚0.5CH2Cl2: C,
55.72; H, 4.97; N, 3.17. IR (ν (KBr)): 3420 (N-H), 3056 (alkene
C-H), 1598 (CdO),20 1566 s, 1541 s (CdC), 1102, 1058 (BF4).
NMR (CDCl3): δ 56.9 (d, 1P, 2J PP ) 32 Hz), 46.9 (d, 1P, 2J PP
)
33 Hz). 1H NMR (CDCl3): δ 2.16 (s, 6H, C6H3(CH3)2), 2.58 (m,
4H, (PCH2CH2P)), 4.10 (m, 1H, PdC(dCH2)), 4.29 (m, 1H, PdC-
(dCH2)), 7.01 (br s, PhNH), 7.17-7-84 (m, 3H, C6H3(CH3)2,
+ 20H, 4 × PC6H5 + 5H, C6H5). 13C{1H} (CDCl3): δ 17.8 (s,
C6H3(CH3)2), 25.8 (br, (PCH2CH2P)), 30.6 (br, (PCH2CH2P)),
113.2 (br, PdC(dCH2)), 126.4-136.4 (several signals assigned
to the phenyl rings of dppe and Xy and phenyl group), 163.2
2
31P{1H} NMR (CDCl3): δ 62.2 (d, 1P, J PP ) 32 Hz), 42.4 (br
2
d, 1P, J PP ) 32 Hz). 1H NMR (CDCl3): δ 1.09 (t, 3H,
2
2
(dd, PdC(dCH2), J CPtrans ) 136 Hz, J CPcis ) 2 Hz), 176.4 (dd,
(NCH2CH3), 3J HH ) 7.0 Hz), 2.13 (s, 6H, C6H3(CH3)2), 2.66 (m,
(CdS), J PC ) 14 Hz, J PC ) 3 Hz). MS (FAB+ m/z (relative
3
3
3
4H, (PCH2CH2P)), 3.33 (q, 2H, HNCH2CH3, J HH ) 7.0 Hz),
intensity)): 785 (100) [M - BF4]+, 504 (10) [(dppe)Pd]+.
4
4
3.89 [dd, 1H, (dppe)PdC(dCH2), J PH ) 19.0 Hz, J P′H ) 13.0
4
4
Hz), 4.85 (dd, 1H, (dppe)PdC(dCH2), J PH ) 5.0 Hz, J PH
)
Syn th esis of [P d {C(dCH2)N(Xy)C(dS)NHMe}(d p p p )]-
[BF 4] (7). Methyl isothiocyanate (0.016 g, 0.23 mmol) was
added to a stirring solution of Pd{C(Me)dNXy}(Cl)(dppp) (0.15
g, 0.21 mmol) in CH2Cl2 (25 mL). AgBF4 (0.04 g, 0.21 mmol)
was added to the reaction mixture as a solid. AgCl immediately
precipitated from the yellow solution. The reaction mixture
was stirred for a further 10 min, after which time the AgCl
was filtered off. The mixture was concentrated under reduced
pressure to 10 mL, and hexane was added until the solution
turned cloudy. The solution was then filtered, and then the
solvent was removed under reduced pressure. The solid residue
was washed with diethyl ether (20 mL) to produce a fine white
powder (which was characterized as 7). Yield: 0.12 g; 0.15
mmol; 69%. Anal. Found: C, 56.68; H, 5.00; N, 3.41. Calcd for
unresolved), 7.12-7-28 (m, 4H, C6H3(CH3)2 + EtNH), 7.40-
7.88 (m, 20H, PC6H5). 13C{1H} (CDCl3): δ 14.2 (s, NCH2CH3),
17.8 (s, C6H3(CH3)2), 22.5 (br, (PCH2CH2P)), 31.5 (br, (PCH2-
CH2P)), 36.6 (s, NCH2CH3), 103.9 (br, PdC(dCH2)), 125.8-
136.8 (several signals assigned to the phenyl rings), 160.7 (dd,
2
2
(dppe)PdC(dCH2), J PCtrans ) 138 Hz, J PCcis ) unresolved),
163.7 (br, (CdO)). MS (FAB+; m/z (relative intensity)): 721
(100) [M - BF4]+, 504 (16) [(dppe)Pd]+.
Syn th esis of [P d {C(dCH2)N(Xy)C(dO)NHP h }(d p p e)]-
[BF 4] (4). Phenyl isocyanate (26.1 µL, 0.24 mmol) was added
to a stirring solution of Pd{C(Me)dNXy}(Cl)(dppe) (0.15 g, 0.22
mmol) in CH2Cl2 (25 mL). AgBF4 (0.043 g, 0.22 mmol) was
added as a solid to the reaction mixture. AgCl immediately
precipitated from the yellow solution. The reaction mixture
was stirred for a further 10 min. The reaction mixture was
left to stir for 12 h, after which time the precipitated AgCl
was filtered off to give a clear yellow solution. A yellow product
was obtained (and characterized as 4) by the reduction of the
solvent to 10 mL and addition of hexane (15 mL). Yield: 0.13
g; 0.18 mmol; 81%. Anal. Found: C, 60.14; H, 4.93; N, 3.18.
Calcd for C43H41P2N2OBF4Pd: C, 60.27; H, 4.82; N, 3.27. IR
(ν (KBr)): 3321 (N-H), 3056 (alkene C-H), 1593w (CdO),19
1555s, 1533s (CdC), 1102, 1064 (BF4). 31P{1H} NMR (CDCl3):
C
39H41P2PdN2SBF4: C, 56.78; H, 5.01; N, 3.41. IR (ν (KBr)):
3386 (N-H), 3054 (alkene C-H), 1560s (CdC), 1262m (Cd
S), 1099, 1057 (BF4). 31P{1H} NMR (CDCl3): δ -1.8 (d, 1P,
2
1
2J PP ) 63 Hz), 14.0 (d, 1P, J PP ) 63 Hz). H NMR (CDCl3): δ
1.93 (s, 6H, C6H3(CH3)2), 2.01 (m, 2H, (PCH2CH2CH2P)), 2.55
(m, 4H, (PCH2CH2CH2P)), 2.87 (d, 3H, HNCH3, 3J HH ) 4.5 Hz),
4
4
3.89 (dd, 1H, PdC(dCH2), J PH ) 7.0 Hz, J P′H ) unresolved),
4.18 (dd, 1H, PdC(dCH2), 4J PH ) 17.5 Hz, 4J P′H ) unresolved),
5.39 (m, 1H, CH3NH), 7.12-7-24 (m, 3H, C6H3(CH3)2), 7.32-
7.74 (m, 20H, 4 × PC6H5). 13C{1H} (CDCl3): δ 17.6 (s, C6H3-
(CH3)2), 18.7 (s, (PCH2CH2CH2P)), 24.5 (dd, (PCH2CH2CH2P),
2
2
δ 43.8 (d, 1P, J PP ) 32 Hz), 62.8 (d, 1P, J PP ) 32 Hz). 1H
1J PC ) 25 Hz, 2J P′C ) 5 Hz), 28.6 (dd, (PCH2CH2CH2P), 1J PC
)
NMR (CD2Cl2): δ 2.22 (s, 6H, C6H3(CH3)2), 2.58 (m, 4H,
31 Hz, 2J PC ) 12 Hz), 32.2 (s, (N-CH3)), 111.5 (dd, PdC(dCH2),
3J PCtrans ) 16 Hz, 3J PCcis ) 6 Hz), 128.8-136.2 (several signals
assigned to the phenyl rings of dppe and Xy group), 163.8 (dd,
4
(PCH2CH2P)), 3.48 (dd, 1H, (dppe)PdC(dCH2), J PH ) 6.5 Hz,
4J P′H ) unresolved], 4.02 (dd, 1H, (dppe)PdC(dCH2), J PH
)
4
18 Hz, 4J PH ) 13 Hz), 6.45 (s br, 1H, NH), 7.1-7-78 (m, 28H,
2
2
PdC(dCH2), J CPtrans ) 138 Hz, J CPcis ) 5 Hz), 175.5 (dd, (Cd
S), J PC ) 14 Hz, J PC ) 3 Hz). MS (FAB+ m/z (relative
3
3
(17) (a) Ru¨lke, R. E.; Ernsting, J . M.; Spek, A. L.; Elsevier, C. J .;
van Leeuwen, P. W. N. M.; Vrieze, K. Inorg. Chem. 1993, 32, 5769. (b)
Ladipo, F. T.; Anderson, G. K. Organometallics 1994, 13, 303.
(18) (a) Appleton, T. G.; Bennett, M. A.; Tomkins, I. B. J . Chem.
Soc., Dalton Trans. 1976, 439. (b) Dekker, G. P. C. M.; Elsevier, C. J .;
Vrieze, K. Organometallics 1992, 11, 1589.
intensity)): 723 (100) [M - BF4]+, 504 (9) [(dppe)Pd]+.
Syn th esis of P d (P h )(I)(d p p e) (8). 1,2-Bis(diphenylphos-
phino)ethane (0.95 g, 2.40 mmol) was added to a solution of
Pd(Ph)(I)(PPh3)2 (2.0 g, 2.40 mmol) in toluene (65 mL). A
precipitate formed after ca. 2 min. The mixture was allowed
to stir for 1 h and then filtered. The resulting filtrate was
washed with toluene (20 mL) and diethyl ether (20 mL).
Yield: 1.25 g; 1.7 mmol; 74%. 31P{1H} NMR (CDCl3): δ 49.5
(19) Fitton, P.; J ohnson, M. P.; McKeon, J . E. J . Chem. Soc., Chem.
Commun. 1968, 6.
(20) The CdO stretching frequency is unusually low; however, this
is not unprecedented for five-membered palladacycles where the oxygen
of a carbonyl group coordinates to the metal center. See for example:
(a) Brumbaugh, J . S.; Whittle, R. R.; Parvez, M.; Sen, A. Organome-
tallics 1990, 9, 1735. (b) Markies, B. A.; Rietveld, M. H. P.; Boersman,
J .; Spek, A. L.; van Koten, G. J . Organomet. Chem. 1992, 424, C12.
2
2
(d, 1P, J PP ) 28 Hz), 34.5 (d, 1P, J PP ) 28 Hz). 1H NMR
(CDCl3): δ 2.28 (m, 4H, (PCH2CH2P)), 6.67 (m, 3H, (3,4,5-Pd-