S. K. Armstrong, R. J. Cross, L. J. Farrugia, D. A. Nichols, A. Perry
FULL PAPER
the reaction had gone to completion as indicated by TLC. The
reaction mixture was quenched with EtOAc and then satd. aq. pot-
assium sodium tartrate solution was added. The mixture was fil-
solution of 11 produced yellow prisms suitable for X-ray analysis.
1H NMR: δ ϭ 3.08Ϫ3.15 (m, 8 H, CH2P), 4.00Ϫ4.05 (m, 8 H,
CH2O), 6.70 (d, J ϭ 2.3 Hz, 4 H, C1,8 H), 6.85 (dd, J ϭ 8.8, 2.4 Hz,
tered, extracted with EtOAc, dried (Na2SO4) and concentrated to 4 H, C3,6 H), 7.42 (t, J ϭ 7.6 Hz, 16 H, Ph o-H), 7.50 (t, J ϭ
give diol 8 (3.79 g, 74%). A portion was recrystallised from meth-
7.4 Hz, 8 H, Ph p-H), 7.54 (d, J ϭ 8.9 Hz, 4 H, C4,5 H), 7.81 (dt,
anol to give diol 8 as a white microcrystalline solid: m.p. 151Ϫ152
J ϭ 7.0, 5.6 Hz, 16 H, Ph m-H). 13C NMR: δ ϭ 28.9 (CH2P), 62.4
1
°C [ref.[16] 152Ϫ153 °C]. H NMR: δ ϭ 2.04 (t, J ϭ 6.1 Hz, 2 H, (t, J ϭ 4 Hz, CH2O), 105.0 (C3,6), 115.8 (C1,8), 123.6 (C4a), 127.6
OH), 4.03 (td, J ϭ 4.2, 5.3 Hz, 4 H, CH2OH), 4.20 (t, J ϭ 4.5 Hz,
(t, J ϭ 5 Hz, Ph m-C), 128.3 (C4,5) 128.8 (Ph ipso-C), 130.1 (Ph p-
4 H, CH2CH2OH), 7.03 (dd, J ϭ 8.8, 2.5 Hz, 2 H, C3,6 H), 7.07 C), 133.0 (t, J ϭ 6 Hz, Ph o-C), 134.9 (C8a), 156.1 (C2,7). 31P{1H}
(d, J ϭ 2.4 Hz, 2 H, C1,8 H), 7.68 (d, J ϭ 8.9 Hz, 2 H, C4,5 H).
NMR: δ ϭ 9.00 (J ϭ 2563 Hz). IR: ν˜ ϭ 3053 w, 2919 w, 1631 s,
13C NMR: δ ϭ 61.5 (CH2OH), 69.2 (CH2CH2OH), 106.3 (C3, C6), 1513 m, 1435 s, 1253 m, 1209 s, 1158 m, 1101 m, 740 m, 691 s. MS:
116.3 (C1, C8), 125.2 (C4a), 129.3 (C4, C5), 135.4 (C8a), 157.2 (C2, m/z (%) ϭ 1701 (1.8) [Pt2Cl4(DPEN)2ϩ], 1665 (1.3) [Mϩ Ϫ Cl], 1628
C7). IR: ν˜ ϭ 3334 br, 2931 w, 2882 w, 1631 s, 1387 m, 1213 s, 1081 (0.8) [Mϩ Ϫ 2Cl]. HRMS: calculated for C76H69Cl4O4P4Pt2:
m, 838 m. MS: m/z (%) ϭ 248 (77) [Mϩ], 204 (35), 160 (100).
1701.2200; found 1701.2217.
2,7-Bis(2Ј-hydroxyethoxy)naphthalene bis(methanesulfonate)ester
cis,cis-[Pt2Cl4(DPEN)2] (12). By Addition of an Excess of Phos-
phane: A solution of DPEN (5; 150 mg, 0.26 mmol) in dichlorome-
thane (8 mL) was added dropwise to a solution of [PtCl2(SMe2)2]
(10; 67 mg, 0.17 mmol) in toluene (90 mL) and dichloromethane
(15 mL) and the mixture was stirred for 18 h at room temperature.
The white precipitate formed was collected by filtration to obtain
cis,cis-[Pt2Cl4(DPEN)2] (12; 104 mg, 72%). Recrystallisation from
a concentrated chloroform solution of 12 gave colourless prisms.
1H NMR: δ ϭ 2.88Ϫ2.94 (m, 8 H, CH2P), 4.56 (quintet, J ϭ
6.4 Hz, 8 H, CH2O), 6.76 (d, J ϭ 2.2 Hz, 4 H, C1,8 H), 6.83 (dd,
J ϭ 8.8, 2.3 Hz, 4 H, C3,6 H), 7.22 (br t, J ϭ 6.9 Hz, 16 H, Ph o-
H), 7.37 (t, J ϭ 7.3 Hz, 8 H, Ph p-H), 7.48 (d, J ϭ 8.9 Hz, 4 H,
C4,5 H), 7.57, (dd, J ϭ 8.1, 10.7 Hz, 16 H, Ph m-H). 13C NMR:
δ ϭ 30.3 (5-line m,[27] JPϪC ϭ 22 Hz, CH2P), 64.8 (CH2O), 107.2
(C3,6), 116.3 (C1,8), 124.9 (C4a), 128.8 (t, J ϭ 5 Hz, Ph m-C), 129.4
(C4,5), 130.1 (4 line m,[27] JPϪC ϭ 32 Hz, Ph i-C), 131.5 (br. s, p-
C), 133.7 (t, J ϭ 5 Hz, o-C), 135.9 (C8a), 156.6 (C2). 31P{1H} NMR:
(9): Methanesulfonyl chloride (1.6 mL, 21 mmol) and triethylamine
(2.9 mL, 21 mmol) were added to a solution of diol 8 (2.17 g,
8.75 mmol) in THF (100 mL) and the mixture was stirred for
30 min at room temperature. The reaction mixture was then filtered
and the solvent removed. The residue was dissolved in EtOAc,
washed with water, dried (Na2SO4) and concentrated. The crude
product was recrystallised from dichloromethane and methanol to
give dimesylate 9 as colourless plates (3.09 g, 87%): m.p. 134Ϫ135
°C. 1H NMR: δ ϭ 3.12 (s, 6 H, CH3S), 4.36Ϫ4.38 (m, 4 H,
CH2CH2OS), 4.64Ϫ4.66 (m, 4 H, CH2OS), 7.01Ϫ7.05 (m, 4 H, C3,6
H, C1,8 H), 7.70 (d, J ϭ 8.7 Hz, 2 H, C4,5 H). 13C NMR: δ ϭ 37.8
(CH3SO2), 65.8 (CH2), 67.9 (CH2), 106.5 (C3, C6), 116.3 (C1, C8),
125.0 (C4a), 129.5 (C4, C5), 135.5 (C8a), 156.7 (C2, C7). IR: ν˜ ϭ
3025 w, 2941 w, 1629 s, 1517 m, 1353 s, 1256 m, 1216 s, 1171 s,
1069 m, 1024 m, 981 s, 930 s, 822 s. MS: m/z (%) ϭ 404 (57) [Mϩ],
123 (100) [C2H4OMsϩ], 79 (28) [SO2CH3ϩ]. C16H20O8S2 (404.45):
calcd. C 47.51, H 4.98; found C 47.49, H 4.88.
˜
δ ϭ 6.49 (PPh2, JPt-P ϭ 3627 Hz). IR: ν ϭ 1631 s, 1436 m, 1209
m, 694 m. MS: m/z (%) ϭ 1701 (2.5) [Pt2Cl4(DPEN)2ϩ], 1665 (13)
[Mϩ Ϫ Cl], 1629 (2) [Mϩ Ϫ 2Cl]. HRMS: calculated for
C76H68Cl3O4P4Pt2: 1665.2433; found 1665.2432. C76H68Cl4O4P4Pt2
(1701.3): calcd. C 53.7, H 4.03; found C 52.9, H 3.97.
DPEN (5): n-Butyllithium (2.5 solution in hexanes, 2.3 mL,
5.75 mmol) was added to
a solution of diphenylphosphane
(1.0 mL, 5.75 mmol) in THF (6 mL). After stirring at room temper-
ature for 15 minutes, a solution of dimesylate 9 (1.04 g, 2.57 mmol)
in THF (60 mL) was added and the mixture stirred overnight. The
solvent was removed and the residue dissolved in dichloromethane,
washed with water, dried (MgSO4) and concentrated. The crude
product was recrystallised from ethyl acetate and pet. ether and
washed with pentane to give DPEN (5) as white needles (1.15 g,
cis,cis-[Pt2Cl4(DPEN)2] (12). By Inverse Addition: A solution of
[PtCl2(SMe2)2] (10; 167 mg, 0.43 mmol) in dichloromethane (5 mL)
was added dropwise over 5 minutes to a stirred solution of DPEN
(5; 250 mg, 0.43 mmol) in dichloromethane (8 mL). After 7 mi-
nutes, the solvent was removed to give a white solid (414 mg) con-
1
77%): m.p. 137Ϫ138 °C. H NMR: δ ϭ 2.65 (t, J ϭ 7.7 Hz, 4 H,
1
sisting largely of cis,cis-[Pt2Cl4(DPEN)2] (12; identified by H and
CH2P), 4.22 (q, J ϭ 7.5 Hz, 4 H, CH2O), 6.80 (d, J ϭ 2.2 Hz, 2
H, C1,8 H), 6.90 (dd, J ϭ 8.9, 2.3 Hz, 2 H, C3,6 H), 7.35Ϫ7.42 (m,
12 H, Ph), 7.51Ϫ7.55 (m, 8 H, Ph), 7.60 (d, J ϭ 8.9 Hz, 2 H, C4,5
H). 13C NMR: δ ϭ 28.3 (d, J ϭ 13 Hz, CH2P), 65.2 (d, J ϭ 27 Hz,
CH2O), 106.0 (s, C3, C6), 116.3 (s, C1, C8), 124.3 (s, C4a), 128.6 (d,
J ϭ 7 Hz, Ph m-C), 128.8 (s, Ph p-C), 129.0 (s, C4, C5), 132.7 (d,
J ϭ 19 Hz, Ph o-C), 135.7 (s, C8a), 137.9 (d, J ϭ 12 Hz, Ph i-C),
31P NMR spectroscopy and by MS) together with small quantities
of higher oligomers.
cis,cis-[Pt2Cl4(DPPN)2] (13): A solution of [PtCl2(SMe2)2] (10;
128 mg, 0.33 mmol) in dichloromethane (4 mL) was added drop-
wise over 5 minutes to a solution of DPPN (4; 200 mg, 0.33 mmol)
in dichloromethane (4.5 mL). After 7 minutes the solvent was re-
moved to give cis,cis-[Pt2Cl4(DPPN)2] (13) as a white solid (281 mg,
97%) which contained small quantities of a closely similar com-
pound, presumed from NMR and MS evidence to be a cis,cis,cis-
trimer. Recrystallisation from dichloromethane produced 13 as col-
ourless prisms suitable for X-ray analysis. 1H NMR (CD2Cl2): δ ϭ
2.20Ϫ2.30 (m, 8 H, CH2CH2P), 2.45Ϫ2.55 (m, 8 H, CH2P), 4.15
31
1
˜
156.9 (s, C2, C7). P{ H} NMR: δ ϭ Ϫ22.8 (s, PPh2). IR: ν ϭ
3066 w, 2914 w, 1630 s, 1514 m, 1433 s, 1211 s, 1168 m, 1018 m,
834 m, 741 s, 697 s. MS: m/z (%) ϭ 584 (4) [Mϩ], 553 (5) [Mϩ
Ϫ
CH3O], 371 (23) [Mϩ Ϫ C2H4PPh2], 341 (42) [Mϩ Ϫ C2H4PPh2],
328 (21), 212 (83) [C2H3PPh2ϩ], 183 (100) [C13H11Oϩ]. HRMS: cal-
culated for C38H34O2P2: 584.2034; found 584.2037.
trans,trans-[Pt2Cl4(DPEN)2] (11): A solution of DPEN (5; 250 mg, (t, J ϭ 6.1 Hz, 8 H, CH2O), 6.91 (dd, J ϭ 2.4, 8.8 Hz, 4 H,
0.43 mmol) in dichloromethane (8 mL) was added dropwise over 5 C3,6 H), 7.10Ϫ7.14 (m, 16 H, Hs meta to P), 7.21 (s, 4 H, C1,8-H),
minutes to a solution of [PtCl2(SMe2)2] (10; 167 mg, 0.43 mmol) in 7.29 (t, J ϭ 7.0 Hz, 8 H, Hs para to P), 7.41 (dd, J ϭ 8.2, 10.0 Hz,
dichloromethane (5 mL). The mixture was stirred at room temper- 16 H, Hs ortho to P), 7.62 (d, J ϭ 8.9 Hz, 4 H, C4,5 H). 31P{1H}
ature for 5 min and then the solvent was removed. Column chroma- NMR: δ ϭ 7.18 (J ϭ 3646 Hz). MS: m/z (%) ϭ 1757 (1.3) [Pt2-
tography (silica, CH2Cl2) of the crude product mixture gave 11 as
Cl4(DPPN)2ϩ], 1721 (9.5) [Pt2Cl3(DPPN)2ϩ], 1685 (2.5) [Pt2Cl2-
a yellow solid (37 mg, 10%). Slow diffusion of Et2O into a CH2Cl2 (DPPN)2ϩ].
148
Eur. J. Inorg. Chem. 2002, 141Ϫ151