Table 1 Products for the thermal decomposition of the platinacyclooctane compounds 5a and 5b at 180 ◦C for 2 h
Products observeda (%)
Complex
Medium
1-Heptene
2-Heptene
1,6-Heptadiene
n-Heptane
Cycloheptane
5a
5b
Solid
Toluene
Solid
45
43
50
43
14
22
20
13
9
<1
2
32
35
28
40
—
—
—
—
Toluene
3
a Products were analysed by GC and GC-MS.
In conclusion, we have shown that it is possible, at least with
platinum, to prepare even membered ring metallacycloalkane
compounds in good yields through a ring closing metathesis
reaction, and that such compounds are quite thermally stable.
Currently, we are exploring the interesting chemical properties
of these compounds to determine reaction pathways that are
available to metallacycloalkanes. We are also investigating similar
compounds with other metals as well as larger membered ring
metallacycloalkanes.
134; 31P NMR: d 3.35 (s) (JPt-P = 1601 Hz). Anal. calcd for C34H40P2Pt:
C, 57.87; H, 5.71. Found: C, 58.16; H, 5.89%. m/z : 705.7 (M+), 607.5
(M − C7H14). 5b (dppe): yield 68%; mp 206–208 ◦C (decomp.). 1H NMR:
d 7.22–7.95 (m, 20H, Ph), 2.23–2.49 (m, 4H, P–CH2), 0.61–2.16 (m, 14H,
CH2); 13C NMR: d 14, 15, 29, 30, 32, 36, 128, 129, 130, 132, 133, 134; 31
P
NMR: d 45.46 (s) (JPt-P = 1623 Hz). Anal. calcd for C33H38P2Pt: C, 57.30;
H, 5.54. Found: C, 57.56; H, 5.79%. m/z : 691.7 (M+), 593.5 (M − C7H14).
§ Crystallographic data for 1a (CCDC number 630919): C37H44P2Pt, M =
745.75 g mol−1, triclinic, space group P1, a = 13.3653(1◦) A, b = 13.9950(1)
¯
˚
◦
◦
˚
˚
A, c = 18.3542(1) A, a = 88.302(1) , b = 75.629(1) , c = 89.361(1) ,
3
V = 3324.19(4) A , Z = 4, qcalcd = 1.490 g cm−3, T = 213(2) K, l =
˚
◦
◦
4.341 mm−1, F(000) = 1496, 1.15 < 2h < 26.02 , k(Mo-Ka) = 0.71073 A,
crystal size 0.18 × 0.18 × 0.15 mm. Intensity data were collected with a
Nonius KappaCCD diffractometer. 80402 reflections, 13036 independent
(Rint = 0.0380, empirical absorption correction (SADABS),12 structure
solution using direct methods (SHELXS-97),12 structure refinement on F2
using full-matrix least-squares procedures (SHELXL-97),12 R1 = 0.0265
[I > 2r(I)], wR2 = 0.0586 (all data), GOF = 1.087, max./min. residual
˚
Acknowledgements
The authors thank Johnson Matthey (London), Anglo Platinum
Corporation, C* Change, NRF, UCT for financial support, and
Feng Zheng for the thermal decomposition studies.
electron density = 1.212/−0.720 e A−3. Crystallographic data for 3b
˚
(CCDC number 630920): C35H40P2Pt, M = 717.70 g mol−1, triclinic, space
¯
˚
˚
˚
group P1◦, a = 10.2728(2) A, b = 10.9231(2) A, c = 13.9720(2) A, a =
◦
◦
3
˚
82.127(1) , b = 77.640(1) , c = 85.733(1) , V = 1515.39(5) A , Z = 2,
Notes and references
qcalcd = 1.573 g cm−3, T = 113(2) K, l = 4.758 mm−1, F(000) = 716, 2.71◦ <
◦
˚
‡ Spectroscopic data (all at 298 K, CDCl3): 1a (dppp): This compound was
2h < 25.67 , k(Mo-Ka) = 0.71073 A, crystal size 0.06 × 0.07 × 0.07 mm.
Intensity data were collected with a Nonius KappaCCD diffractometer.
32938 reflections, 5693 independent (Rint = 0.0670), empirical absorption
correction (SADABS), structure solution using direct methods (SHELXS-
97), structure refinement on F2 using full-matrix least-squares procedures
(SHELXL-97), R1 = 0.0360 [I > 2r(I)], wR2 = 0.0960 (all data), GOF =
prepared according to the reported procedure.6 1b (dppe): yield 96%; mp
◦
1
84–85 C (decomp.). H NMR: d 7.35–7.92 (m, 20H, Ph), 5.52–5.71 (m,
=
=
2H, CH), 4.68–4.86 (m, 4H, CH2), 2.01–2.23 (m, 4H, P–CH2), 1.17–
1.89 (m, 12H, CH2); 31P NMR: d 45.7 (s) (JPt-P = 1639 Hz). Anal. calcd
for C36H42P2Pt: C, 59.09; H, 5.79. Found: C, 58.98; H, 5.69%. m/z : 731.7,
662.6, 593.5. 2a (dppp): yield 70%; mp 154–157 ◦C (decomp.). 1H NMR:
−3
˚
1.092, max./min. residual electron density = 1.508/−2.513 e A
.
=
d 7.22–7.84 (m, 20H, Ph), 5.68–5.90 (m, 1H, CH), 4.67–5.05 (m, 2H,
CH2), 2.65–3.12 (m, 6H, P–CH2), 0.62–1.33 (m, 6H, CH2); 31P NMR: d
1 B. Blom, H. Clayton, M. Kilkenny and J. R. Moss, Adv. Organomet.
Chem., 2006, 54, 149.
=
−1.6 (s) (JPt-P = 3845 Hz). Anal. calcd for C31H33P2PtCl: C, 53.97; H, 4.95.
Found: C, 54.04; H, 4.92. m/z = M+, 712.1; [M − Cl]+, 676.6; [(dppp)Pt]+,
607.1. 2b (dppe): yield 45%; mp 205–208 ◦C (decomp.). 1H NMR: d 6.96–
8.02 (m, 20H, Ph), 5.42–5.58 (m, 1H, CH), 4.50–4.77 (m, 2H, CH2),
1.89–2.25 (m, 4H, P-CH2), 0.69–1.81 (m, 6H, CH2); 31P NMR: d 42.40
(d), 43.33 (d) (JPt-P = 4442 and 1595 Hz). Anal. calcd for C31H33P2PtCl: C,
53.3◦4; H, 4.76. Found: C,53.46; H, 4.72%. 3a (dppp): yield 76%; mp 95–
104 C (decomp.). 1H NMR: d 6.93–7.78 (m, 20H, Ph), 5.68–6.27 (m, 2H,
2 R. H. Grubbs, Tetrahedron, 2004, 60, 7177 and references therein.
3 (a) T. Agapie, S. J. Schofer, J. A. Labinger and J. E. Bercaw, J. Am.
Chem. Soc., 2004, 125, 1304; (b) A. Bollmann, K. Blann, J. T. Dixon,
F. M. Hess, E. Killian, H. Maumela, D. S. McGuinness, D. H. Morgan,
A. Neveling, S. Otto, M. Overett, A. M. Z. Slawin, P. Wasserscheid and
S. Kuhlmann, J. Am. Chem. Soc., 2004, 126, 14712; (c) M. J. Overett,
K. Blann, A. Bollmann, J. T. Dixon, D. Haasbroek, E. Killian, H.
Maumela, D. S. McGuinness and D. H. Morgan, J. Am. Chem. Soc.,
2005, 127, 10723; (d) A. K. Tomov, J. J. Chirinos, D. J. Jones, R. J. Long
and V. C. Gibson, J. Am. Chem. Soc., 2005, 127, 10166.
4 (a) K. Dralle, N. L. Jaffa, T. L. Roex, J. R. Moss, S. Travis, N. D.
Watermayer and A. Sivaramakrishna, Chem. Commun., 2005, 3865;
(b) A. Sivaramakrishna, H. Clayton, C. Kauschula and J. R. Moss,
Coord. Chem. Rev., 2007, 251, 1294.
=
=
=
=
CH), 4.74–5.26 (m, 4H, CH2), 1.82–2.22 (m, 6H, P-CH2), 0.61–1.79
(m, 10H, CH2); 31P NMR: d 2.57, 2.68 (d), 4.25, 4.13 (d) (JPt-P = 1674 and
1689 Hz). m/z : 731.6 (M+), 676.7, 662.6, 607.5. 3b (dppe): yield 79%; mp
162–166 ◦C (decomp.). 1H NMR: d 7.24–7.95 (m, 20H, Ph), 5.54–5.83 (m,
=
=
2H, CH), 4.46–5.15 (m, 4H, CH2), 2.25–2.46 (m, 4H, P-CH2), 0.81–
2.19 (m, 10H, CH2); 31P NMR: d 45.98, 45.91 (d), 45.76, 45.70 (d) (JPt-P
=
1685 and 1635 Hz). Anal. calcd for C35H40P2Pt: C, 58.57; H, 5.62. Found:
C, 58.92; H, 5.57%. m/z : 717.72 (M+), 662.6, 648.6, 593.5. 4a (dppp):
yield 70%; mp 164–168 ◦C (decomp.). 1H NMR: d 7.14–7.81 (m, 20H,
5 A. Sivaramakrishna, Hong Su and J. R. Moss, Angew. Chem., Int. Ed.,
2007, 46, 3541.
=
Ph), 5.27–5.47 (m, 2H, CH), 0.84–2.17 (m, 6H, P-CH2), 0.37–1.77 (m,
6 (a) T. Mahamo, F. Zheng, A. Sivaramakrishna, G. S. Smith and J. R.
Moss, J. Organomet. Chem., 2008, 693, 103; (b) A. Sivaramakrishna,
B. L. Watson, F. Zheng and J. R. Moss, Polyhedron, 2008, accepted;
(c) A. Sivaramakrishna, J. R. Moss, E. Hager, H. Clayton, T. Mahamo,
F. Zheng, L. L. M. Mbatha and M. M. Mogorosi, unpublished results.
7 A. J. Nawara, T. Shima, F. Hampel and J. A. Gladysz, J. Am. Chem.
Soc., 2006, 128, 4962 and references therein.
8 F. H. Allen, O. Kennard, D. G. Watson, R. Taylor, International Tables
for Crystallography, ed. A. J. C. Wilson, Kluwer Academic Publishers,
Dordrecht, 1992, vol. C.
10H, CH2); 31P NMR: d 3.23 and 3.51 (JPt-P = 1574 and 1631 Hz). Anal.
calcd for C34H38P2Pt: C, 58.03; H, 5.44. Found: C, 58.16; H, 5.88%. m/z :
◦
703.7 (M+), 607.5. 4b (dppe): yield 64%; mp 138–142 C (decomp.). H
1
=
NMR: d 7.18–8.02 (m, 20H, Ph), 5.12–5.29 (m, 2H, CH), 2.28–2.47 (m,
4H, P–CH2), 0.48–1.92 (m, 10H, CH2); 31P NMR: d 45.05, 45.5 (JPt-P
=
1619 and 1617 Hz). Anal. calcd for C33H36P2Pt: C, 57.47; H, 5.26. Found:
C, 57.68; H, 5.34%. 5a (dppp): yield 82%; mp 134–136 ◦C (decomp.). 1H
NMR: d 6.96–7.80 (m, 20H, Ph), 2.34–3.43 (m, 6H, P–CH2), 0.88–2.35 (m,
14H, CH2); 13C NMR: d 14, 15, 20, 26, 27, 29, 30, 33, 36, 37, 128, 129, 133,
2230 | Dalton Trans., 2008, 2228–2231
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