1J(31P77Se) 170.4, 2J(31P31P) 51.3 Hz], 254.2 [P(1), d, 1J(31P77Se) 203.0,
2J(31P77Se) 48.1 Hz]. For 5: 1H NMR (toluene-d8): d 0.80 (s, 18H, tBu), 0.97
(s, 9H, tBu). 31P{1H} NMR (121.49 MHz, CDCl3): d 74.5 [P(1) and P(2),
d, 2J(31P31P) 7.2, 1J(31P77Se) 317.4, 2J(31P77Se) 0.4, 14.0 Hz], 236.0 [P(3),
t, 1J(31P77Se) 177.8, 2J(31P77Se) 42.1, 2J(31P77Se) 14.5 Hz]. 77Se{1H}
NMR: d 256.5 [Se(4), dt, 1J(31P77Se) 177.8, 2J(31P77Se) 23.2 Hz], 514.3
[Se(3), d, 2J(31P77Se) 52.5], 67.6 [Se(1) and Se(2), m, 1J(31P77Se) 317.4,
2J(31P77Se) 40.3, 2J(31P77Se) 15.4 Hz].
‡ Crystal data: 4 C15H27P3Se3, M = 537.16, monoclinic, space group P21/n
(no. 14), a = 10.7751(3), b = 16.2798(7), c = 11.6992(3) Å, b =
102.264(2)°, U = 2005.4(1) Å3, Z = 4, Dc = 1.78 Mg m23, crystal
dimensions 0.2 3 0.1 3 0.1 mm, F(000) = 1056, T = 293(2) K, Mo-Ka
radiation, l = 0.71073 Å. Data collection Kappa CCD, 16312 reflections
collected, 5787 independent (Rint = 0.0498), R1 = 0.038, wR2 = 0.083 for
4569 reflections with I > 2s(I), R1 = 0.055, wR2 = 0.090 for all data.
although homonuclear S–S bonds are common in monocyclic
(RP)xSy systems, analogous Se–Se bonded compounds are
rare.16
Interestingly, the cage compound 5 undergoes an unexpected
1
reaction with [PtCl2(PMe3)]2. It was anticipated that simple h -
coordination would occur, via either the P or Se lone pair
electrons, however the platinum(II) fragment also unexpectedly
inserts into the Se(1)–Se(2) bond of 5 as well as undergoing
ligation to Se(3) of the four-membered P(3)C(3)Se(3)C(2) ring,
to afford the novel deep-red Pt(IV) complex [PtCl2(PMe3)-
P3Se4C3But3] 7 (55.8%).§
¯
5: C15H27P3Se4, M = 16.12, triclinic, space group P1 (no. 2), a =
9.902(2), b = 10.340(4), c = 12.760(4) Å, a = 69.17, b = 71.11(2), g =
61.57°, U = 1054.6(6) Å3, Z = 2, Dc = 1.94 Mg m23, crystal dimensions
0.35 3 0.20 3 0.20 mm, F(000) = 596, T = 173(2) K, Mo-Ka radiation,
l = 0.71073 Å. Data collection CAD4. Of the total 5081 independent
reflections measured, the final indices for 3999 reflections with I > 2s(I)
were R1 = 0.037, wR2 = 0.076 and R1 = 0.057, wR2 = 0.088 for all
data.
¯
7: C18H36Cl2P4PtSe4, M = 958.18, rhombohedral, space group R3 (no.
148), a = 34.5455(6), c = 16.7221(2) Å, U = 17282.4(5) Å3, Z = 18, Dc
= 1.66 Mg m23, crystal dimensions 0.2 3 0.1 3 0.1 mm, F(000) = 8136,
T = 293(2) K, Mo-Ka radiation, l = 0.71073 Å. Data collection Kappa
CCD, 41518 reflections collected, 10989 independent (Rint 0.0553), R1 =
0.039, wR2 = 0.083 for 7872 reflections with I > 2s(I), R1 = 0.069, wR2
= 0.095 for all data.
crystallograhic files in .cif format.
The latter was fully structurally characterised by a single
crystal X-ray diffraction study‡ and its molecular structure is
shown in Fig. 3.
§ NMR data for 7: 31P{1H} NMR (121.49 MHz, CDCl3): d 62.7 [P(1) and
P(2), m, 2J(31P31P) 14.9, 1J(31P77Se) 330.5, 2J(31P31P) 6.0 Hz]; 35.4 [P(3),
m, 2J(31P31P) 13.1, 2J(31P31P) 6.0 Hz], 28.1 [P(4), m, 1J(31P195Pt) 2221,
2J(31P31P) 14.9, 2J(31P31P) 5.9 Hz]. 195Pt{1H} NMR:
[1J(31P195Pt) 2209 Hz].
d 23630.4
1 K. B. Dillon, F. Mathey and J. F. Nixon, Phosphorus: The Carbon Copy,
John Wiley and Sons, Chichester, 1998, pp. 1–366 and references
therein.
2 Carbocyclic and Heterocyclic (P, As, N) Cage Compounds and their
Building Blocks: Synthesis, Structure, Mechanism and Theory, ed. K. K.
Laali and B. Halton, JAI Press Inc., Stamford, CT, 1999.
3 A. Mack and M. Regitz, Chem. Ber., 1997, 130, 823.
4 V. Caliman, P. B. Hitchcock and J. F. Nixon, J. Chem. Soc., Chem.
Commun., 1995, 1661.
5 P. B. Hitchcock, J. F. Nixon and N. Sakarya, Chem. Commun., 1996,
2751.
6 V. Caliman, P. B. Hitchcock and J. F. Nixon, J. Organomet. Chem.,
1997, 536, 273.
7 V. Caliman, P. B. Hitchcock, J. F. Nixon, L. Nyula´szi and N. Sakarya,
Chem. Commun., 1997, 1305.
8 V. Caliman, P. B. Hitchcock, J. F. Nixon and N. Sakarya, Bull. Soc.
Chim. Belg., 1996, 105, 675.
9 M. Regitz and S. Krill, Phosphorus, Sulfur Silicon Relat. Elem., 1996,
115, 99.
10 V. Caliman, P. B. Hitchcock and J. F. Nixon, Heteroatom Chem., 1998,
9, 1.
11 F. G. N. Cloke, P. B. Hitchcock, P. Hunnable, J. F. Nixon, L. Nyula´szi,
E. Niecke and V. Thelen, Angew. Chem., Int. Ed., 1998, 37, 1083.
12 V. Caliman, P. B. Hitchcock and J. F. Nixon, Chem. Commun., 1998,
1537.
Fig. 3 Molecular structure of 7. Selected bond lengths (Å) and angles (°):
Pt–P(4) 2.3103(13), Pt–Cl(1) 2.4120(14), Pt–Cl(2) 2.4241(12), Pt–Se(2)
2.4434(6), Pt–Se(1) 2.4493(5), Pt–Se(3) 2.4679(5), Se(1)–P(1) 2.2266(13),
Se(2)–P(2) 2.2175(14), Se(4)–P(3) 2.2301(16), Se(4)–C(1) 2.007(5),
Se(3)–C(2) 2.026(5), Se(3)–C(3) 2.030(5), P(1)–C(1) 1.869(5), P(1)–C(3)
1.869(5), P(2)–C(1) 1.885(5), P(2)–C(2) 1.872(6): P(3)–C(2) 1.890(6),
P(3)–C(3) 1.889(5); P(4)–Pt–Cl(1) 88.03(5), P(4)–Pt–Cl(2) 92.33(5),
Cl(1)–Pt–Cl(2) 89.28(5), P(1)–Pt–Se(2) 93.57(4).
13 M. D. Francis, D. E. Hibbs, P. B. Hitchcock, M. B. Hursthouse, C.
Jones, T. Mackewitz, J. F. Nixon, L. Nyula´szi, M. Regitz and N.
Sakarya, J. Organomet. Chem., 1999, 580, 156.
14 F. G. N. Cloke, P. B. Hitchcock, J. F. Nixon, D. J. Wilson, F. Tabellion,
U. Fishbeck, F. Preuss, M. Regitz and L. Nyula´szi, Chem. Commun.,
1999, 2363.
We thank the Turkish government for a research grant (for
N. S.) and the British Council for financial support for part of
this work.
15 S. M. F. Asmus, U. Bergstrasser and M. Regitz, Synthesis, 1999,
1642.
16 P. Lonnecke and R. Blachnik, Phosphorus, Sulfur Silicon Relat. Elem.,
1997, 131, 191 and references therein.
Notes and references
† NMR data: for 4: 31P{1H} NMR (121.49 MHz, CDCl3): d 80.7 [P(2), dd,
2J(31P31P) 53.3, 1J(31P77Se) 208.4, 2J(31P31P) 53.3 Hz], 21.5 [P(3), d,
1746
Chem. Commun., 2000, 1745–1746