[Pt{PPh CH᎐C(Ph)NN᎐C(Ph)O}{PPh CH C(Ph)᎐NNHC-
(᎐O)Ph}] (12). A solution containing the phosphine II (96 mg,
residue to give 16 as a pale yellow solid. Yield 96 mg, 78%.
Found: C, 61.75; H, 4.0; N, 5.25; C54H44N4O2P2ptؒ0.2CH2Cl2
requires C, 61.7; H, 4.2; N, 5.3%. MS (FAB) m/z: 1038 ([M +
᎐
᎐
᎐
2
2
2
᎐
0.23 mmol) and [PtCl2(NCMe)2] (40 mg, 0.11 mmol) in
dichloromethane (5 cm3) was warmed for 10 min, then treated
with triethylamine (0.1 cm3) and put aside for 20 min. The solv-
ent was then removed and methanol added to the residue to
give (12) as an orange solid. Yield 66 mg, 58%. Found: C, 61.85;
H, 4.1; N, 5.5; C54H44N4O2P2PtؒCH3OH requires C, 61.75;
H, 4.5; N, 5.25%. MS (FAB) m/z: 1038 ([M + 1]+). IR (cmϪ1):
ν(N–H) = 3460m. 31P-{1H} NMR (36.2 MHz, CDCl3),
1]+). IR (cmϪ1): ν(C᎐C) = 1595m and ν(N–H) = 3320m. 31P-{1H}
᎐
NMR (36.2 MHz, CDCl3), δP (ppm): Ϫ16.6(s), 1J(PtP) = 3311.
2
1H NMR (100 MHz, CDCl3), δH (ppm): 4.15 [1H, dd, J(PH)
4
3
4.6, J(HH) 1.3, J(PtH) 37.8, PCH᎐] and 10.90 [1H, br, NH,
᎐
exchanges with D2O].
[PtCl{PPh CH[C(CO Me)᎐CH(CO Me]᎐C(But)N–N᎐
᎐
᎐
᎐
2
2
2
1
1
δP (ppm): 3.4 (d), J(PtP) = 3108; 8.0 (d), J(PtP) = 3557 and
2J(PP) = 14. 1H NMR (100 MHz, CDCl3), δH (ppm): 3.93 [2H,
d, 2J(PH) 10.0, 3J(PtH) 38.3, CH2] and 4.81 [1H, d, 2J(PH) 10.5,
C(Ph)O }] (17). A solution of the chloroplatinum() complex 2
(70 mg, 0.11 mmol) and dimethyl acetylenedicarboxylate (15 µl,
0.12 mmol) in chloroform (2 cm3) was treated with triethyl-
amine (15 µl) and then put aside for 12 h. The solvent was then
removed and methanol added to the residue to give 17 as a pale
pink solid. Yield 47 mg, 55%. Found: C, 47.8; H, 4.15; Cl, 4.7;
N, 3.45; C31H33ClN2O5PPt requires C, 48.05; H, 4.3; Cl, 4.6; N,
3.6%. MS (FAB) m/z: 775 ([M + 1]+) and 738 (M–HCl). IR
3J(PtH) 18.9, PCH᎐].
᎐
[Pd{PPh CH᎐C(But)NHNC(᎐O)Ph} ] (13). A solution con-
᎐
᎐
2
2
taining the phosphine I (110 mg, 0.27 mmol) and [PdCl2-
(NCPh)2] (50 mg, 0.14 mmol) in dichloromethane (2 cm3) was
treated with an excess of triethylamine (0.1 cm3, 0.72 mmol)
and then put aside for 3 h. The solvent was then removed and
methanol added to the residue to give 13 as an orange solid.
Yield 52 mg, 41%. Found: C, 65.75; H, 5.95; N, 6.4;
C50H52N4O2P2Pd requires C, 66.05; H, 5.75; N, 6.15%. MS
(cmϪ1): ν(C᎐O) = 1730s and ν(Pt–Cl) = 345m. 31P-{1H} NMR
᎐
(36.2 MHz, CDCl3), δP (ppm): 21.3(s), 1J(PtP) = 4089. 1H NMR
(100 MHz, CDCl3), δH (ppm): 1.42 (9H, s, But), 3.22 (3H, s,
2
3
OMe), 3.68(3H, s, OMe), 5.56 [1H, d, J(PH) 13.6, J(PtH)
38.4, PCH] and 6.58 [1H, d, J(PH) 4.3, ᎐CHCO ]. 13C-{1H}
4
᎐
2
(FAB) m/z: 909 ([M + 1]+). IR (cmϪ1): ν(C᎐C) = 1605m and
NMR (100.6 MHz, CDCl3) δC: 28.8 (3C, s, CMe3), 39.3 [1C, d,
᎐
3J(PC) 7.3, CMe3], 52.3 (1C, s, OMe), 52.9 (1C, s, OMe), 57.5
ν(N–H) = 3325m. 31P-{1H} NMR (36.2 MHz, CDCl3), δP
1
1
[1C, d, J(PC) 34.8, CHP], 131.2 (1C, s, ᎐CHCO Me), 163.9
᎐
2
(ppm): 5.2(s). H NMR (100 MHz, CDCl3), δH (ppm): 1.16
(9H, s, But), 3.68 [1H, dd, 2J(PH) 2.0, 4J(HH) 1.3, PCH᎐]
(1C, s, C᎐N), 165.3 [1C, d, J(PC) 2.8, C᎐N], 172.9 [1C, s, C᎐O]
᎐
᎐
᎐
᎐
and 8.63 [1H, br, NH, exchanges with D2O]. 13C-{1H} NMR
and 180.6 [1C, d, J(PC) 3.6, C᎐O). Molecular weight in chloro-
᎐
form = 767 Daltons; calc. for C31H33ClN2O5PPt 775 Daltons.
(100.6 MHz, CDCl3) δC: 29.8 (3C, s, CMe3), 37.1 (1C, s, CMe3),
1
62.3 [1C, d, J(PC) 73.6, ᎐CHP], 161.8 (1C, s, ᎐CN) and 173.5
᎐
᎐
[PdCl{PPh CH[C(CO Me)᎐CH(CO Me]᎐C(But)N–N᎐
᎐
᎐
᎐
2
2
2
(1C, s, C᎐O).
᎐
C(Ph)O}] (18). Compound 1 (710 mg, 1.3 mmol) and dimethyl
acetylenedicarboxylate (0.27 ml, 2.2 mmol) in chloroform
(10 cm3) was treated with triethylamine (0.30 ml) and the solu-
tion put aside for 5 h. The solvent was then removed and
methanol added to the residue to give 18 as a pale pink solid.
Yield 0.45 g, 51%. Found: C, 53.95; H, 4.6; Cl, 5.3; N, 4.15;
C31H33ClN2O5PPd requires C, 54.3; H, 4.85; Cl, 5.1; N, 4.1%.
[Pt{PPh CH᎐C(But)NHNC(᎐O)Ph} ] (14). A solution con-
᎐
᎐
2
2
taining the phosphine I (310 mg, 0.77 mmol) and [PtCl2(cod)]
(144 mg, 0.38 mmol) in dichloromethane (10 cm3) was treated
with an excess of triethylamine (0.1 cm3, 0.72 mmol) and was
put aside for 6 h. The solvent was then removed and methanol
added to the residue to give 14 as a pale yellow solid.
Yield 88 mg, 47%. Found: C, 58.9; H, 5.3; N, 5.4;
C50H52N4O2P2Ptؒ2CH3OH requires C, 58.8; H, 5.7; N, 5.25%.
MS (FAB) m/z: 685 (Mϩ) and 649 (M–HCl). IR (cmϪ1): ν(C᎐O)
᎐
= 1730s and ν(Pd–Cl) = 340m. 31P-{1H} NMR (36.2 MHz,
CDCl3), δP (ppm): 52.1(s). 1H NMR (100 MHz, CDCl3),
δH (ppm): 1.41 (9H, s, But), 3.26 (3H, s, OMe), 3.67 (3H, s,
OMe), 5.60 [1H, d, 2J(PH) 14.7, PCH] and 6.69 [1H, d,
4J(PH)4.4, ᎐CHCO ]. 13C-{1H} NMR (100.6 MHz, CDCl3) δC:
MS (FAB) m/z: 998 ([M + 1]+). IR (cmϪ1): ν(C᎐C) = 1595m
᎐
and ν(N–H) = 3325m. 31P-{1H} NMR (36.2 MHz, CDCl3), δP
(ppm): Ϫ17.1(s), 1J(PtP) = 3274. 1H NMR (100 MHz,
CDCl3), δH (ppm): 1.12 (9H, s, But), 3.78 [1H, dd, 2J(PH)
᎐
2
28.8 (3C, s, CMe3), 39.5 [1C, d, 3J(PC) 9.5, CMe3], 52.3 (1C, s,
2.14, 4J(HH) 1.4, 3J(PtH) 37.8, PCH᎐] and 8.20 [1H, br,
᎐
OMe), 52.8 (1C, s, OMe), 57.4 [1C, d, 1J(PC) 27.5, CHP], 130.9
3J(PtH) 23.1, NH, exchanges with D2O]. 13C-{1H} NMR
(1C, s, ᎐CHCO Me), 163.8 (1C, s, C᎐N), 165.1 [1C, d, J(PC)
᎐
᎐
2
(100.6 MHz, CDCl3) δC: 29.8 (3C, s, CMe3), 37.1 (1C, s,
3.1, C᎐N], 172.5 [1C, d, J(PC) 3.5, C᎐O] and 178.4 [1C, d, J(PC)
᎐
᎐
1
CMe ), 62.9 [1C, d, J(PC) 81.3, ᎐CHP], 161.3 (1C, s, ᎐CN)
᎐
᎐
3
3.4, C᎐O].
᎐
and 173.2 (1C, s, C᎐O).
᎐
[PtBr{PPh CH[C(CO Me)᎐CH(CO Me]᎐C(But)NN᎐C(Ph)-
᎐
᎐
᎐
2
2
2
[Pd{PPh CH᎐C(Ph)NHNC(᎐O)Ph} ] (15). A solution con-
᎐
᎐
2
2
O}] (19). A solution containing the chloroplatinum() complex
17 (118 mg, 0.15 mmol) and LiBr (415 mg, 4.8 mmol) in acet-
one (20 cm3) was put aside for 15 h. The solvent was then
removed and methanol added to the residue to give 19 as a
yellow solid. Yield 70 mg, 57%. Found: C, 44.6; H, 3.8; N, 3.35;
C31H33BrN2O5PPtؒ0.3CH2Cl2 requires C, 44.5; H, 4.0; N, 3.3%.
taining the phosphine II (109 mg, 0.26mmol) and
[PdCl2(NCPh)2] (50 mg, 0.13 mmol) in dichloromethane (5 cm3)
was treated with triethylamine (0.1 cm3, 0.7 mmol) and the
mixture put aside for 12 h. The solvent was then removed and
methanol added to the residue to give 15 as an orange solid.
Yield 100 mg, 81%. Found: C, 67.75; H, 4.45; N, 5.9;
C54H44N4O2P2Pdؒ0.2CH2Cl2 requires C, 67.4; H, 4.6; N, 5.7%.
MS (FAB) m/z: 820 (M Ϫ 1). IR (cmϪ1): ν(C᎐O) = 1735s. 31P-
᎐
1
{1H} NMR (36.2 MHz, CDCl3), δP (ppm): 20.9(s), J(PtP) =
MS (FAB) m/z: 949 ([M + 1]+). IR (cmϪ1): ν(C᎐C) = 1595m and
4011. 1H NMR (100 MHz, CDCl3), δH (ppm): 1.48(9H, s, But),
3.35 (3H, s, OMe), 3.71(3H, s, OMe), 5.67 [1H, d, 2J(PH) 13.1,
3J(PtH) 22.5, PCH] and 6.65 [1H, d, 4J(PH) 4.3, ᎐CHCO ].
᎐
ν(N–H) = 3325m. 31P-{1H} NMR (36.2 MHz, CDCl3), δP
1
(ppm): 5.7 (s). H NMR (100 MHz, CDCl3), δH (ppm): 4.10
᎐
2
[1H, dd, 2J(PH) 2.7, 4J(HH) 1.7, PCH᎐] and 8.09 [1H, br, NH,
᎐
[PtI{PPh CH[C(CO Me)᎐CH(CO Me]᎐C(But)NN᎐C(Ph)-
exchanges with D2O].
᎐
᎐
᎐
2
2
2
O}] (20). A solution containing the chloroplatinum() complex
17 (111 mg, 0.14 mmol) and NaI (429 mg, 2.9 mmol) in acetone
(20 cm3) was put aside for 15 h. The solvent was then removed
and methanol added to the residue to give 20 as an orange solid.
This was recrystallised from CH2Cl2–MeOH. Yield 90 mg, 74%.
Found: C, 41.7; H, 3.7; N, 3.8; C31H33IN2O5PPtؒ0.5CH2Cl2
[Pt{PPh CH᎐C(Ph)NHNC(᎐O)Ph} ] (16). A solution con-
᎐
᎐
2
2
taining the phosphine II (104 mg, 0.25 mmol) and
[PtCl2(NCPh)2] (58 mg, 0.12 mmol) in dichloromethane (5 cm3)
was treated with triethylamine (0.1 cm3) and then put aside for
20 h. The solvent was then removed and methanol added to the
1960
J. Chem. Soc., Dalton Trans., 2002, 1954–1962