S. Dey et al. / Inorganic Chemistry Communications 10 (2007) 1385–1390
1389
[9] R. Uson, J. Fornies, M. Tomas, I. Ara, J. Chem. Soc. Dalton Trans.
(1989) 1011.
[10] W. Baratta, P.S. Pregosin, A. Bacchi, G. Pelizzi, Inorg. Chem. 33
(1994) 4494.
[11] M. Capdevilla, W. Clegg, P. Gonzalez-Duarte, B. Harris, I. Mira, J.
Sola, I.C. Taylor, J. Chem. Soc. Dalton Trans. (1992) 2817.
[12] V.K. Jain, S. Kannan, R.J. Butcher, J.P. Jaisinski, J. Chem. Soc.
Dalton Trans. (1993) 1503.
[13] A. Singhal, V.K. Jain, B. Varghese, E.R.T. Tiekink, Inorg. Chim.
Acta 285 (1999) 190.
[14] A. Singhal, V.K. Jain, A. Klein, M. Niemeyer, W. Kaim, Inorg.
Chim. Acta 357 (2004) 2134.
[15] S.W.A. Fong, T.S.A. Horr, J. Chem. Soc. Dalton Trans. (1999)
639.
[16] S. Dey, V.K. Jain, A. Knoedler, A. Klein, W. Kaim, S. Zalis, Inorg.
Chem. 41 (2002) 2864.
[17] [Pd2Cl3(TeCH2CH2NMe2)(PMePh2)2] (1a): (a) To an acetone solution
(10 cm3) of [PdCl(TeCH2CH2NMe2)(PMePh2)] (70 mg, 0.129 mmol),
a solution of [Pd2Cl2(l-Cl)2(PMePh2)2] (49 mg, 0.065 mmol) was
added and the whole was strirred for 2 h and the solvent was
evaporated under vacuum, the residue was recrystallized from
acetone–hexane (69 mg, 58%). Found C, 39.6; H, 4.2; N, 1.5%. Calcd.
for C30H36P2NTeCl3Pd2: C, 39.2; H, 4.0; N, 1.5%. 1H NMR (acetone-
d6) d: 1.98 (br, TeCH2); 2.31 (d, 12 Hz, PCH3); 2.75 (s, NMe2); 4.26
(br, NCH2–); 7.43–7.59 (br, m); 7.70–7.76 (m) (Ph). 31P{1H} NMR
(acetone-d6) d: 14.1 (s, br). When the complex was left in solution
(acetone-d6 or CDCl3) at room temperature for sometime new peaks at
19.4, 8.1 (due to cis and trans [PdCl2(PMePh2)2]) and 3.1 ppm
appeared. (b) To a dichloromethane solution (20 cm3) of [Pd2Cl2(l-
Cl)2(PMePh2)2] (156 mg, 0.207 mmol) was added freshly prepared
methanolic solution of NaTeCH2CH2NMe2 (prepared from
(Me2NCH2CH2Te)2 (41 mg, 0.10 mmol) and NaBH4 (8 mg,
0.21 mmol)) with stirring at room temperature. After 3 h the solvents
were evaporated in vacuo and the brown residue was extracted with
dichloromethane (3 · 8 cm3). The solution was passed through a
Florisil column and the solvent was removed in vacuo. The residue was
recrystallized from an acetone–hexane mixture (96 mg, 51%); m.p.
145 ꢁC. Found C, 39.7; H, 4.2; N, 1.6%. Calcd. for
[20] [Pt3Cl4(SeCH2CH2NMe2)2(PEt3)2] (2a): To a dichloromethane solu-
tion (8 cm3) of [PtCl2(PhCN)2] (124 mg, 0.26 mmol) was added a
dichloromethane solution (10 cm3) of [PtCl(SeCH2CH2NMe2)(PEt3)]
(270 mg, 0.54 mmol) with stirring which continued for 4 h. The
solvent was evaporated under vacuum and the residue was extracted
with acetone (3 · 5 cm3) and passed through a Florisil column, and
the solution on cooling to ꢀ5 ꢁC gave yellow crystals (yield 178 mg,
52%), m.p. 164 ꢁC. Found C, 20.0; H, 4.1; N, 2.3%. Calcd. for
C20H50P2N2Se2Cl4Pt3 Æ 0.5 Me2CO: C, 19.9; H, 4.1; N, 2.2%. 1H
NMR in CDCl3d: 1.16 (m, PCH2CH3), 2.11 (br, PCH2); 2.76 (br,
NMe2); 3.43 (br, NCH2/SeCH2). 31P{1H} NMR in CDCl3 d: 3.1 (s,
1J(195Pt–31P) = 3364 Hz). 195Pt{1H} NMR in CDCl3 d: ꢀ4254 (d,
1J(195Pt–31P) = 3355 Hz), ꢀ3145 (PtCl2). When the solution was left
for 24 h, other peaks also appeared indicating disproportionation of
the complex.
[21] [Pt3Cl4(SeCH2CH2NMe2)2ðPPrn3Þ2] (2b): Prepared analogously to
[Pt3Cl4(SeCH2CH2NMe2)2(PEt3)2] by adding [PtCl2(PhCN)2]
(76 mg, 0.16 mmol) to [PtCl(SeCH2CH2NMe2)ðPPrn3Þ] (175 mg,
0.32 mmol) in acetone–dichloromethane and recrystallized as yellow
powder in 45% yield, m.p. 190ꢁC. Found C, 23.3; H, 4.7; N, 2.2%.
Calcd. for C26H62P2N2Se2Cl4Pt3: C, 23.1; H, 4.6; N, 2.1%. Mass: m/z
1350 [M]+; 1314 [M–Cl]. 1H NMR (CDCl3) d: 1.06 (t, 7.1 Hz,
PCH2CH3), 1.66 (br, PCH2CH2); 2.16–2.45 (PCH2, SeCH2); 2.72, 2.89
(each br s, NMe2); 3.06, 3.50 (each br s, NCH2). 31P{1H} NMR
(CDCl3) d: ꢀ5.7 (1J(Pt–P) = 3335 Hz). 77Se{1H} NMR (CDCl3) d:
232.7 (br). 195Pt{1H} NMR (CDCl3) d: ꢀ4236 (d, 1J(Pt–P) =
2
3336 Hz); ꢀ3149 (d, J(Pt–Pt) = 495 Hz).
[22] [Pt2PdCl4(SeCH2CH2NMe2)2ðPPrn3Þ2] (2c): Prepared analogously to
[Pt3Cl4(SeCH2CH2NMe2)2(PEt3)2] by adding [PdCl2(PhCN)2] (65 mg,
0.17 mmol) with [PtCl(SeCH2CH2NMe2)ðPPrn3Þ] (185 mg, 0.34 mmol)
in acetone and recrystallized from dichloromethane–hexane in 41%
yield, m.p. 187 ꢁC. Found C, 24.3; H, 4.8; N, 2.3%. Calcd. for
C
26H62P2N2Se2Cl4Pt2Pd: C, 24.8; H, 5.0; N, 2.2%. Mass: m/z 1225
[M-Cl]. 1H NMR (CDCl3) d: 1.04 (br, PCH2CH2CH3), 1.62 (br,
PCH2CH2); 1.88 (br, PCH2); 2.48 (br, SeCH2); 2.64 (s, NMe2); 2.95
(br, NCH2). 31P{1H} NMR (CDCl3) d: ꢀ5.3 (1J(Pt–P) = 3320 Hz)
(small amount of starting material was present + a small peak at
ꢀ6.2, 1J = 3300 Hz). 77Se{1H} NMR (CDCl3) d: 249.8. 195Pt{1H}
NMR (CDCl3) d: ꢀ4206 (d, 1J(Pt–P) = 3310 Hz); ꢀ4060 (d, 1J(Pt–
P) = 3534 Hz) (small); ꢀ4126 (d, 1J(Pt–P) = 3297 Hz) (small).
C
30H36P2NTeCl3Pd2: C, 39.2; H, 4.0; N, 1.5%.
[18] [Pt2Cl3(TeCH2CH2NMe2)(PMePh2)2] (1b): Prepared by the reaction
between [Pt2Cl2(l-Cl)2(PMePh2)2] (57 mg, 0.063 mmol) and
[PtCl(TeCH2CH2NMe2)(PMePh2)] (77 mg, 0.122 mmol) in acetone.
The product was recrystallized from an acetone–hexane mixture at
ꢀ5 ꢁC as pale yellow crystals (yield 86 mg, 64%); m.p. 180ꢁC. Found
C, 33.2; H, 3.3; N, 1.3%. Calcd. for C30H36P2NTeCl3Pt2: C, 32.9; H,
3.3; N, 1.3%. 1H NMR in CDCl3 d: 1.95 (br, TeCH2); 2.22 (d, 11.3 Hz);
2.37 (d, 11.4 Hz) (for PMe); 2.56, 3.13 (each s, NMe2); 3.66 (m), 4.05
(m) (NCH2); 7.20–7.80 (m, Ph). 31P{1H} NMR in CDCl3 d: ꢀ11.6
(1J = 3409 Hz, 3J(Pt–P) = 74 Hz); ꢀ5.2(1J = 3634 Hz, 3J(Pt–
[23] [PdPtCl3(SeCH2CH2NMe2)(PPh3)2] (1d): In an attempt to
prepare [Pd2PtCl4(SeCH2CH2NMe2)2(PPh3)2], a reaction between
PtCl2(dmso)2 (63 mg, 0.15 mmol) and [PdCl(SeCH2CH2NMe2)-
(PPh3)] (164 mg, 0.30 mmol) in dmso-CH2Cl2 (5:15 cm3) was carried
out. After stirring the reactants for 2 h, the solvent was evaporated
and the residue was dissolved in acetone (15 cm3). Within a few
minutes from this solution a poorly soluble product identified as
[PdCl(SeCH2CH2NMe2)]3 (m.p. 216–218 ꢁC; 1H NMR (CDCl3) d:
2.82 (br, s, NMe2 + SeCH2), 3.06 (br, s, NCH2)) was separated out.
P) = 74.6 Hz).
125Te{1H}
NMR
in
CDCl3
d:
ꢀ1310
The filtrate was dried in vacuo to give a yellow powder of
(1J(195Pt–125Te) = 331 Hz). 195Pt{1H} NMR in CDCl3 d: ꢀ4400 (d,
1J = 3650 Hz; 2J(195Pt–195Pt) = 568 Hz); ꢀ4460 (d, 1J = 3457 Hz;
2J(195Pt–195Pt) = 555 Hz).
[PdPtCl3(SeCH2CH2NMe2)(PPh3)2] (1d) (76 mg, 47% yield). Found
C, 44.8; H, 3.5; N, 1.2%. Calcd. for C40H40P2NSeCl3PdPt: C, 44.3;
H, 3.7; N, 1.3%. 1H NMR in CDCl3 d: 2.60–3.20 (m, due to
complex as well as [PdCl(SeCH2CH2NMe2)]3), 7.20–7.90 (m, Ph).
31P{1H} NMR in CDCl3 d: 25.9 (Pd–P); 8.0 (1J(Pt–P) = 3771 Hz)
also contains cis-PtCl2(PPh3)2 (d 14.9; 1J(Pt–P) = 3672 Hz). Single
crystals of 1d were obtained from CDCl3 solution in NMR
tube.
[19] [PdPtCl3(SeCH2CH2NMe2)(PEt3)2] (1c): To an acetone solution
(20 cm3) of [PdCl(SeCH2CH2NMe2)(PEt3)] (174 mg, 0.42 mmol),
[Pt2Cl2(l-Cl)2(PEt3)2] (161 mg, 0.21 mmol) was added with stirring
which continued for 2 h. The solvent was evaporated in vacuo to give
a yellow residue which was recrystallized from acetone–hexane in 52%
yield, m.p. 168 ꢁC. Found C, 23.8; H, 5.1; N, 2.0%. Calcd. for
[24] S. Dey, V.K. Jain, M. Seger, W. Kaim (unpublished results).
[25] Crystal data for [PdCl(SeCH2CH2NMe2)(PPh3)PtCl2(PPh3)] (1d):
C
16H40P2NSeCl3PtPd: C, 24.2; H, 5.1; N, 1.8%. Mass: m/z 848
ꢀ
[Pt2Cl2(SeCH2CH2NMe2)(PEt3)2]; 812 [Pt2Cl(SeCH2CH2NMe2)-
(PEt3)2]; 760 [PdPtCl2(SeCH2CH2NMe2)(PEt3)2]. 1H NMR (CDCl3)
d: 1.15–1.25 (m, PCH2CH3), 1.86–2.19 (m, PCH2–); 2.65 (minor), 2.71
(major) (SeCH2); 2.81 (br, s, NMe2); 3.05 (br, NCH2). 31P{1H} NMR
(CDCl3) d: 3.8 (1J(Pt–P) = 3346 Hz); 24.5 (s, Pd–P) (for heteronuclear
complex); other small resonances were present at: 3.2 (1J(Pt–
P) = 3505 Hz), 2.4 (1J(Pt–P) = 3328 Hz); 28.6 (s, Pd–P), 32.4 (s, Pd–
P).
C
40H40Cl3NP2Pd0.79Pt1.21Se, M = 1102.10, triclinic, space group P1,
˚
˚
˚
a = 10.8318(15) A, b = 14.555(2) A, c = 16.050(3) A, a = 97.938(3)ꢁ,
3
˚
b = 95.464(7)ꢁ, c = 110.507(7)ꢁ, V = 2319.0(6) A , T = 93(2) K, Z =
2, Dc = 1.576 g/cm3, l = 5.004 mmꢀ1, F(000) = 1064, k = 0.71073 A,
˚
data/restraints/parameters = 9144/186/372. The final wR2 = 0.4511,
R1 [I > 2r(I)] = 0.1968.
[26] H.C. Clark, G. Ferguson, V.K. Jain, M. Parvez, Inorg. Chem. 24
(1985) 1477.