y Synthetic and analytical details for the starting reagents are
given in the ESI. Synthesis of 3: a 0.5 M benzene solution of
Lu(CH2SiMe3)3(THF)2 (5 mL, 2.5 mmol) was slowly added to a
stirred solution of 1 (956 mg, 2.5 mmol) in benzene (5 mL) at room
temperature. The reaction mixture was then stirred and heated at 45
1C. It gradually changed in colour from orange-red to dark yellow.
After 2 d a small amount of precipitate formed that was filtered off and
the resulting solution was reduced in volume to approx. 5 mL and very
slowly cooled down to 10 1C for crystallization. After several weeks
light yellow crystals formed. The product was filtered off, washed with
pre-cooled benzene (2 mL) and dried under vacuum. Yield 0.72 g
(46%). 1H NMR (300 MHz, C6D6, +23 1C): d 7.89–6.95 (br m, Aryl-
groups and solvated C6H6), 3.60 (br s, CH2–O, THF), 2.75 (br s, CH3–
O), 1.70 (br t, CH2–CH2–O, THF). 31P NMR (121.5 MHz, C6D6,
+23 1C): d 12.2 (br s). Elemental analysis was calculated for
C60H56Lu2O4P2(C6H6)4, C 64.45%, H 5.15%, Lu 22.35%, observed
C 63.92%, H 5.28%, Lu 22.17%. Synthesis of 5: a 0.5 M THF solution
of Y(o-Me2NCH2C6H4)3 (5 mL, 2.5 mmol) was added to a stirred
solution of 1 (956 mg, 2.5 mmol) in toluene (30 mL). The orange
solution was slowly heated to 65 1C and allowed to stir at this
temperature for 5 h, while it gradually deepened in colour and a
bright yellow precipitate deposited. After slow cooling to room
temperature, the dark red solution was decanted and the yellow solid
was washed with toluene (2 ꢃ 5 mL) and dried under high vacuum.
Yield 0.60 g (42%) of C52H40O2P2Y2(C4H8O)(C9H13N). 1H NMR
(300 MHz, C5D5N, +23 1C): d 7.89–7.15 (br m, Aryl-groups), 3.65 (br
s, CH2–O, THF), 3.54 (s, Me2NCH2), 3.45 (br s, CH3–O), 2.19 (s,
Me2N), 1.59 (br t, CH2–CH2–O, THF). 31P NMR (121.5 MHz,
C5D5N, +23 1C): d 36.8. Elemental analysis was calculated for
References
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14 P. L. Watson, J. Chem. Soc., Chem. Commun., 1983, 276.
15 H. Schumann, F. W. Reier and E. Palamidis, J. Organomet. Chem.,
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C65H61NO3P2Y2,
C 68.25%, H 5.37%, N 1.22%, observed C
16 H. Schumann and F. W. Reier, J. Organomet. Chem., 1984, 269,
21.
68.96%, H 5.31%, N 1.22%.
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J. H. Teuben, Organometallics, 1993, 12(9), 3531.
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Chem. Soc., 1990, 112, 5384.
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z Data were collected on a STOE IPDS diffractometer using graphite
monochromated Mo-Ka radiation (l = 0.71073 A). The structures
were solved by direct methods and refined by full-matrix least-squares
techniques against F2 using SHELX-97 software package.25 Crystal
ꢀ
data: for 1: C26H23OP, M = 382.41, triclinic, space group P1, a =
9.746(2) A, b = 10.046(2) A, c = 10.715(2) A, a = 73.76(2)1, b =
85.61(2)1, g = 89.94(2)1, V = 1004.0(3) A3, Z = 2, Dc = 1.265 g
cmꢂ3, m(Mo-Ka) = 0.151 mmꢂ1. T = ꢂ123 1C, crystal dimensions
0.76 ꢃ 0.40 ꢃ 0.08 mm, 6420 reflections were measured, 3401 were
symmetry independent and 2577 were observed [I > 2s(I)], R1
=
22 Poor solubility of 3 at lower temperatures prohibits study of its
dynamic behaviour with NMR in more detail.
0.0376 and wR2 = 0.0945 (all data). CCDC reference number 245413.
For 3: C84H80Lu2O4P2, M = 1565.36, monoclinic, space group P21/c,
a = 14.192(5) A, b = 12.461(4) A, c = 20.490(5) A, b = 105.51(3)1, V
= 3491.6(18) A3, Z = 2, Dc = 1.489 g cmꢂ3, m(Mo-Ka) = 2.908
mmꢂ1. T = ꢂ93 1C, crystal dimensions 0.40 ꢃ 0.28 ꢃ 0.20 mm, 17113
reflections were measured, 4979 were symmetry independent and 2802
were observed [I > 2s(I)], R1 = 0.0843 and wR2 = 0.2278 (all data).
The intensities were corrected for Lorentz polarization and absorption
effects using ABSCOR, a modification of DIFABS (Tmin = 0.366,
23 Two solvate C6H6 molecules per asymmetric unit of 3 and one
solvate THF molecule per asymmetric unit of 5a have been found.
24 See for example: (a) W. J. Evans, J. C. Brady and J. W. Ziller, J.
Am. Chem. Soc., 2001, 123, 7711; (b) S. Arndt, P. M. Zeimentz, T.
P. Spaniol, J. Okuda, M. Honda and K. Tatsumi, Dalton Trans.,
2003, 3622; (c) P. G. Hayes, G. C. Weich, D. J. H. Emslei, C. L.
Noack and W. E Piers, Organometallics, 2003, 22, 1577; (d) S.
Bambirra, D. van Leusen, A. Meetsma, B. Hessen and J. H.
Teuben, Chem. Commun., 2003, 522.
Tmax
C68H72O6P2Y2,
=
0.558).26 CCDC reference number 245412. For 5a:
ꢀ
1225.02, triclinic, space group P1,
M
=
a
=
25 (a) G. M. Sheldrick, Programm for solution of crystal structures,
SHELXL-97, Universitat Gottingen, 1997, 22; (b) G. M. Sheldrick,
12.513(3) A, b = 14.455(3) A, c = 19.023(4) A, a = 86.89(3)1, b =
75.64(3)1, g = 70.68(3)1, V = 3144.4(11) A3, Z = 2, Dc = 1.294 g
cmꢂ3, m(Mo-Ka) = 1.936 mmꢂ1. T = ꢂ73 1C, crystal dimensions 0.45
ꢃ 0.25 ꢃ 0.20 mm, 40601 reflections were measured, 11055 were
¨
¨
Programm for the refinement of crystal structures, SHELXL-97,
Universitat Gottingen, 1997, 22.
26 N. Walker and D. Stuart, Acta Crystallogr., Sect. A, 1983, A39,
¨
¨
symmetry independent and 6310 were observed [I > 2s(I)], R1
=
158.
0.0624 and wR2 = 0.1511 (all data). CCDC reference number 286123.
For crystallographic data in CIF or other electronic format see DOI:
10.1039/b514439f.
ꢀc
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