2
5
0
R
5. Preparation of 6,6 -{(g -dppe)(g -C5Me5)Fe–C C}2-
Notes and references
(2,20-bipyridine) zinc dichloride complex [ZnCl2(6)]
1 C. Lapinte and D. Astruc, J. Chem. Soc., Chem. Commun., 1983,
430.
The metallo-ligand 6 (0.138 g, 0.100 mmol) and zinc dichloride
(0.014 g, 0.100 mmol) were added in a Schlenk tube with
15 mL of CH2Cl2 at 20 1C and stirred for 5 h. The solvent was
removed in vacuo. Infrared analysis of the crude residue
revealed that the reaction was complete, resulting in the almost
quantitative formation of [ZnCl2(6)]. The dark red solid was
extracted with toluene (3 ꢃ 5 mL). The deep red solution was
concentrated to 0.5 mL and the desired complex [ZnCl2(6)]
was precipitated by addition of n-pentane. After decantation,
washing with cold n-pentane (2.5 mL) and drying in vacuum,
[ZnCl2(6)] was isolated as a deep red solid (0.139 g, 91%).
Anal. calcd for C86H84F12Cl2N2P6Fe2Zn: C, 68.07; H, 5.58; N.
1.85%. Found: C, 67.74; H, 5.36; N. 1.77%. ESI MS (m/z):
2 C. Lapinte, D. Catheline and D. Astruc, Organometallics, 1988,
7, 1683.
3 C. Lapinte, D. Catheline and D. Astruc, Organometallics, 1984,
3, 817.
4 C. Roger, P. Hamon, L. Toupet, H. Rabaa, J.-Y. Saillard,
J.-R. Hamon and C. Lapinte, Organometallics, 1991, 10, 1045.
5 N. G. Connelly, M. P. Gamasa, J. Gimeno, C. Lapinte, E. Lastra,
J. P. Maher, N. Le Narvor, A. L. Rieger and P. H. Rieger, J. Chem.
Soc., Dalton Trans., 1993, 2575.
6 N. Le Narvor, L. Toupet and C. Lapinte, J. Am. Chem. Soc., 1995,
117, 7129.
7 F. Paul and C. Lapinte, Coord. Chem. Rev., 1998, 178–180, 427.
8 F. Coat and C. Lapinte, Organometallics, 1996, 15, 477.
9 F. Paul, W. E. Meyer, L. Toupet, H. Jiao, J. A. Gladysz and
C. Lapinte, J. Am. Chem. Soc., 2000, 122, 9405.
10 K. M.-C. Wong, S. C.-F. Lam, C.-C. Ko, N. Zhu, V. W.-W. Yam,
calcd for [M
ꢀ
H]+ [C86H85Cl2N2P4Fe2Zn] 1515.3025,
S. Roue, C. Lapinte, S. Fathallah, K. Costuas, S. Kahlal and
´
J.-F. Halet, Inorg. Chem., 2003, 42, 7086.
found (CH2Cl2) 1515.3035. FT-IR (nKBr, cmꢀ1
) 1981
(vs, CRC), 1586 (s, bipy). NMR 31P (d, C6D6, 81 MHz) 101.6
(s, 4P, dppe).
11 M. I. Bruce, K. Costuas, T. Davin, B. E. Ellis, J.-F. Halet,
C. Lapinte, P. J. Low, K. M. Smith, B. W. Skelton, L. Toupet
and A. H. White, Organometallics, 2005, 24, 3864.
12 S. I. Ghazala, F. Paul, L. Toupet, T. Roisnel, P. Hapiot and
C. Lapinte, J. Am. Chem. Soc., 2006, 128, 2463.
13 P. Hamon, F. Justaud, O. Cador, P. Hapiot, S. Rigaut, L. Toupet,
L. Ouahab, H. Stueger, J.-R. Hamon and C. Lapinte, J. Am.
Chem. Soc., 2008, 130, 17372.
14 Y. Lu, R. Quardokus, C. S. Lent, F. Justaud, C. Lapinte and
S. A. Kandel, J. Am. Chem. Soc., 2010, 132, 13519.
15 N. Le Narvor and C. Lapinte, Organometallics, 1995, 14, 634.
16 M. Guillemot, L. Toupet and C. Lapinte, Organometallics, 1998,
17, 1928.
17 Y. Tanaka, J. A. Shaw-Taberlet, F. Justaud, O. Cador, T. Roisnel,
M. Akita, J.-R. Hamon and C. Lapinte, Organometallics, 2009,
28, 4656.
18 M. Lohan, F. Justaud, T. Roisnel, P. Ecorchard, H. Lang and
C. Lapinte, Organometallics, 2010, 29, 4804.
19 F. Coat, M.-A. Guillevic, L. Toupet, F. Paul and C. Lapinte,
Organometallics, 1997, 16, 5988.
20 T. Weyland, K. Costuas, A. Mari, J.-F. Halet and C. Lapinte,
Organometallics, 1998, 17, 5569.
21 S. Le Stang, D. Lenz, F. Paul and C. Lapinte, J. Organomet.
Chem., 1998, 572, 189–192.
22 S. Le Stang, F. Paul and C. Lapinte, Inorg. Chim. Acta, 1999,
291, 403.
23 F. Paul, F. Malvoti, G. da Costa, S. Le Stang, F. Justaud,
G. Argouarch, A. Bondon, S. Sinbandhit, K. Costuas, L. Toupet
and C. Lapinte, Organometallics, 2010, 29, 2491.
24 S. I. Ghazala, N. Gauthier, F. Paul, L. Toupet and C. Lapinte,
Organometallics, 2007, 26, 2308.
6. X-Ray crystal structure of 6[PF6]2
Single crystals suitable for X-ray crystallography of 6[PF6]2
were obtained as described above and were mounted with
epoxy cement on the tips of glass fibers. The data were
collected on a Bruker-AXS APEXII diffractometer equipped
with a CCD camera and a graphite-monochromated Mo Ka
radiation source (l = 0.71073 A), from the Centre de
Diffractometrie de l’Universte de Rennes 1, France. The
´ ´
structure was solved by direct methods using the SIR-97
program and refined by least-squares on F2 using the
SHELXL-97 program.49 Some residual electron densities were
difficult to modelize and therefore, the SQUEEZE function of
PLATON (Spek, 2003) was used to estimate and remove the
contribution of the electron densities in the solvent region
from observed structure factors. A disordered solvent-free
model was then used in the final refinement. A main cavity
of 477% A3 per unit cell was estimated by the SQUEEZE
procedure, leading to an 81 electrons content, that could
correspond to one molecule of dichloromethane and one
molecule of pentane. Crystal data, data collection, and structure
refinement parameters for 6[PF6]2: empirical formula,
C86H84F12Fe2N2P6ꢂ4(CH2Cl2); formula mass, g molꢀ1, 2155.17;
collection T, K, 150(2); crystal system, triclinic; space group,
25 F. Paul, S. Goeb, F. Justaud, G. Argouarch, L. Toupet, R. Ziessel
and C. Lapinte, Inorg. Chem., 2007, 46, 9036.
26 F. Justaud, G. Argouarch, S. I. Ghazala, L. Toupet, F. Paul and
C. Lapinte, Organometallics, 2008, 27, 4260.
%
P1; a (A), 11.3200(3); b (A), 14.2718(3); c (A), 16.4565(4); a (1),
105.1050(10); b (1), 107.1970(10); g (1), 95.4930(10); V (A3),
2408.64(11), Z, 1; Dcalcd (g cmꢀ3), 1.486; crystal size (mm),
0.25 ꢃ 0.17 ꢃ 012; F(000), 1116; abs. coeff. (mmꢀ1),
695; y range (1), 3.01 to 27.48; range h, k, l, ꢀ14 o h o 14,
ꢀ18 o k o 18, ꢀ21 o l o 21; no. total reflns, 10 989;
no. unique reflns, 9 225; I 4 2s(I); final R, R1 = 0.0761;
wR2 = 0.2255; R indices (all data), R1 = 0.0846; wR2, 0.2322;
goodness of fit, 1.063; largest diff. peak and hole (e Aꢀ3), 2.169
and ꢀ1.77.
27 S. I. Ghazala, F. Paul, L. Toupet and C. Lapinte, J. Organomet.
Chem., 2007, 692, 917.
28 R. Denis, T. Weyland, F. Paul and C. Lapinte, J. Organomet.
Chem., 1997, 545–546, 615.
29 J. Hassan, J. Penalva, L. Lavenot, C. Gozzi and M. Lemaire,
Tetrahedron, 1998, 54, 13793.
30 R. Ziessel, J. Suffert and M. T. Youinou, J. Org. Chem., 1996,
61, 6535.
31 N. Le Narvor and C. Lapinte, J. Chem. Soc., Chem. Commun.,
1993, 357.
32 C. H. Kline Jr. and J. Turkevitch, J. Chem. Phys., 1944, 12, 300.
33 L. Corrsin, B. J. Fax and R. C. Lord, J. Chem. Phys., 1953, 21, 1170.
34 J. K. Wilmshurst and H. J. Bernstein, Can. J. Chem., 1956,
35, 1183.
35 F. Paul, J.-Y. Mevellec and C. Lapinte, J. Chem. Soc., Dalton
Trans., 2002, 1783.
36 D. Astruc, Electron Transfer and Radical Processes in Transition-
Metal Chemistry, VCH, New York, 1995.
Acknowledgements
Dr H. Le Bozec (Rennes) is warmly acknowledged for very
stimulating and fruitful discussions.
c
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New J. Chem., 2011, 35, 2219–2226 2225