R. H. Laitinen et al.
FULL PAPER
[4]
C. J. Elsevier, B. Kowall, H. Kragten, Inorg. Chem. 1995, 34,
4836Ϫ4839.
S. Song, E. C. Alyea, Can. J. Chem. 1996, 74, 2304Ϫ2320.
T. L. Brown, K. J. Lee, Coord. Chem. Rev. 1993, 128, 89Ϫ116.
J. M. Smith, B. C. Taverner, N. J. Coville, J. Organomet. Chem.
1997, 530, 131Ϫ140.
J. A. Miles, M. T. Beeny, K. W. Ratts, J. Org. Chem. 1975, 40,
343Ϫ347.
R. G. Jones, H. Gilman, Org. React. 1951, 6, 339Ϫ356.
L. Hirsivaara, M. Haukka, S. Jääskeläinen, R. H. Laitinen, E.
Niskanen, T. A. Pakkanen, J. Pursiainen, J. Organomet. Chem.,
in press.
product was obtained by extraction of the aqueous phase with di-
ethyl ether. The product (0.60 g, 1.93 mmol, 38.7%) was dried in
vacuo. Single crystals were grown by vapor diffusion of hexane into
a methanol/dichloromethane solution of the pyridylphosphane.
M.p. 122Ϫ123°C. Ϫ 1H NMR (200 MHz, CDCl3): δ ϭ 2.5 (s, 3 H,
[5]
[6]
[7]
[8]
H12), 7.2 (m, 6 H, H6, H8, and H9), 7.4 (t, JHϪH ϭ 7.7 Hz, 2 H,
3
3
4
H4), 7.6 (t, JHϪH ϭ 7.7 Hz, JHϪP ϭ 1.9 Hz, 2 H, H5), 8.7 (d,
[9]
3JHϪH ϭ 4.7 Hz, 2 H, H3). Ϫ 13C{1H} NMR (50 MHz, CDCl3):
[10]
δ ϭ 14.8 (s, 1 C, C12), 123.3 (s, 2 C, C4), 126.5 (d, JCϪP ϭ 8.7 Hz,
2
2
1
2 C, C8), 128.9 (d, JCϪP ϭ 20.3 Hz, 2 C, C6), 132.3 (d, JCϪP
ϭ
[11]
[12]
L. Hirsivaara et al., to be published.
10.2 Hz, 1 C, C7), 136.2 (s, 2 C, C5), 136.6 (d, JCϪP ϭ 2.9 Hz, 2
3
K. R. Dunbar, J. S. Sun, S. C. Haefner, J. H. Matonic, Or-
ganometallics 1994, 13, 2713Ϫ2720.
C, C9), 142.0 (s, 1 C, C10), 150.9 (d, JCϪP ϭ 11.6 Hz, 2 C, C3),
3
[13]
[14]
[15]
[16]
1
164.1 (d, JCϪP ϭ 4.4 Hz, 2 C, C1). Ϫ 31P{1H} NMR (162 MHz,
J. P. Farr, M. M. Olmstead, A. L. Balch, J. Am. Chem. Soc.
1980, 102, 6654Ϫ6656.
CDCl3): δ ϭ Ϫ1.6 (s). Ϫ MS: Exact mass: 310.0727.
A. Maisonnet, J. P. Farr, M. M. Olmstead, C. T. Hunt, A. L.
Balch, Inorg. Chem. 1982, 21, 3961Ϫ3967.
X-ray Crystallography: X-ray diffraction data were collected with
an EnrafϪNonius Kappa-CCD (compounds 1 and 3؊6) or a Nico-
let R3m (compound 2) diffractometer using Mo-Kα radiation (λ ϭ
A. S. C. Chan, C. C. Chen, R. Cao, M. R. Lee, S. M. Peng, G.
H. Lee, Organometallics 1997, 16, 3469Ϫ3473.
J. G. Verkade, L. D. Quin (Eds.), Phosphorus-31 NMR Spec-
troscopy in Stereochemical Analysis, VCH Publishers, Inc., De-
erfield Beach, FL, U.S.A., 1987, p. 88Ϫ92.
˚
0.71073 A). For 2, cell parameters were obtained from 25 automati-
cally centered reflections. Data collection (ω scan mode), data re-
duction, and cell refinement were carried out with the P3/P4 dif-
fractometer program V4.27.[27] For the other compounds, the data
were collected using or combined Ϫω scans with the Collect[28]
data collection program. Denzo and Scalepack[29] programs were
used for cell refinements and data reduction. All structures were
solved by direct methods using either SHELXS-97[30] or SIR-97[31]
programs with the WinGX[32] graphical user interface, or by using
the SHELXTL v5.1[33] program package. Structure refinements
were carried out with SHELXL-97.[34] All non-hydrogen atoms
were refined anisotropically. For compounds 1؊5, the hydrogens
were constrained to ride on their parent atom [Uiso ϭ 1.2(Ceq) for
aromatic hydrogens and Uiso ϭ 1.5(Ceq) for methyl H atoms]. For
compound 6, all hydrogens were located from the difference Four-
ier map and refined isotropically with constant Uiso ϭ 0.05 for
aromatic hydrogens and Uiso ϭ 0.08 for methyl hydrogens. Crystal-
lographic data are summarized in Table 3 and selected bond lengths
and angles are given in Tables 4 and 5.
[17]
S. O. Grim, W. McFarlane, E. F. Davidoff, J. Org. Chem 1967,
31, 781Ϫ784.
[18]
[19]
P. Suomalainen, R. H. Laitinen et al., to be published.
S. O. Grim, A. W. Yankowsky, Phosphorus and Sulfur 1977, 3,
191Ϫ195.
[20]
[21]
Y. Yamashoji, T. Matsushita, M. Tanaka, T. Shono, Polyhedron
1989, 8, 1053Ϫ1059.
R. J. Bowen, A. C. Garner, S. J. Berners-Price, I. D. Jenkins, R.
E. Sue, J. Organomet. Chem. 1998, 554, 181Ϫ184.
T. Allman, R. G. Goel, Can. J. Chem. 1982, 60, 716Ϫ722.
T. T. Derencsenyi, Inorg. Chem. 1981, 20, 665Ϫ670.
C. A. Streuli, Anal. Chem. 1960, 32, 985Ϫ987.
A. Michaelis, Annalen 1896, 293, 249Ϫ257.
[22]
[23]
[24]
[25]
[26]
[27]
W. C. Davies, F. G. Mann, J. Chem. Soc. 1944, 276Ϫ283.
P3/P4 Diffractometer Program V4.27, Siemens Analytical X-ray
Instruments, 1989؊1991.
Collect, Data collection software, EnrafϪNonius, Delft, The
Netherlands, 1998.
[28]
[29]
Z. Otwinowski, W. Minor, Processing of X-ray Diffraction Data
Collected in Oscillation Mode, Methods in Enzymology, Vol.
276, Macromolecular Crystallography, Part A (Eds.: C. W.
Carter, Jr., R. M. Sweet), Academic Press, 1997, p. 307Ϫ326.
G. M. Sheldrick, SHELXS-97, Program for Crystal Structure
Determination, University of Göttingen, Germany, 1997.
A. Altomare, C. Cascarano, C. Giacovazzo, A. Guagliardi, A.
G. G. Moliterni, M. C. Burna, G. Polidori, M. Camalli, R.
Spagna, SIR-97, A Package for Crystal Structure Solution by
Direct Methods and Refinement, University of Bari, Italy, 1997.
L. J. Farrugia, WinGX Ϫ A Windows Program for Crystal Struc-
ture Analysis, University of Glasgow, Scotland, 1998.
G. M. Sheldrick, SHELXTL Version 5.1, Bruker Analytical X-
ray Systems, Inc., Madison, Wisconsin, USA, 1998.
G. M. Sheldrick, SHELXL-97, Program for Crystal Structure
Refinement, University of Göttingen, Germany, 1997.
Received February 8, 1999
[30]
[31]
Crystallographic data (excluding structure factors) for the struc-
tures reported in this paper have been deposited with the Cam-
bridge Crystallographic Data Centre as supplementary publication
nos. CCDC-114003 to CCDC-114008. Copies of the data can be
obtained free of charge on application to CCDC, 12 Union Road,
Cambridge CB2 1EZ, U.K. [Fax: (internat.) ϩ44 (0)1223/ 336033;
E-mail: deposit@ccdc.cam.ac.uk].
[32]
[33]
[34]
[1]
C. A. Tolman, Chem. Rev. 1977, 77, 313Ϫ348.
[2]
C. A. Tolman, J. Am. Chem. Soc. 1970, 92, 2953Ϫ2956.
[3]
C. A. Tolman, J. Am. Chem. Soc. 1970, 92, 2956Ϫ2965.
[I99042]
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