S. Wang et al.
directly, and liquid aldehydes or ketones were distilled before use.
sequent difference Fourier syntheses, and refined anisotropically for all
non-hydrogen atoms by full-matrix, least-squares calculations on F2 by
use of the SHELXTL program package.[19] All hydrogen atoms were re-
fined with use of a riding model.
[17]
[(Me3Si)2N]3Ln
(C4H3NH)[12g] were prepared by literature methods. IR spectra were re-
corded with a SHIMADZU FTIR-8400S spectrometer. 1H NMR and
13C NMR spectra for analyses of compounds were recorded with
A
E
and
2-[(2,6-Me2C6H3)NHCH2]-
ACHTUNGTRENNUNG
a
CCDC-791771 (2), CCDC-791772 (3), CCDC-791773 (4), and CCDC-
791774 (6) contain the supplementary crystallographic data for this
paper. These data can be obtained free of charge from The Cambridge
Bruker AV 300 NMR spectrometer in C6D6 for lanthanide complexes
and in CDCl3 for organic compounds.
Synthesis of {(m-h5:h1):h1--2-[(2,6-Me2C6H3)NCH2]
(2): A toluene (10.0 mL) solution of 2-[(2,6-Me2C6H3)NHCH2]
(1, 0.40 g, 2.00 mmol) was added at room temperature to a toluene
(30.0 mL) solution of [(Me3Si)2N]3Y(m-Cl)Li(THF)3 (1.66 g, 2.00 mmol).
A
ACHTUGNRTNE(NUNG SiMe3)2}2
AHCTUNGTRENNUNG
General Procedures for hydrophosphonylations of aldehydes: A 30.0 mL
Schlenk tube was charged under dried argon with the dinuclear rare
earth metal amido complex 4 (20.0 mg, 0.02 mmol) and diethyl phosphite
(3.32 g, 24 mmol), either under solvent-free conditions or in toluene
(2.0 mL), and the relevant aldehyde (20.0 mmol) was then added to the
mixture. The resulting mixture was allowed to stir at RT for 5 min. After
the reaction was complete, the reaction mixture was hydrolyzed with
water (3 mL), extracted with ethyl acetate (3ꢂ10 mL), dried over anhy-
drous Na2SO4, and filtered. After the solvent had been removed under
reduced pressure, the final products were further purified by washing
with hexane. The full characterization data for the resulting products can
be found in the Supporting Information.
A
ACHTUNGTRENNUNG
After the reaction mixture had been stirred at room temperature for 6 h,
the mixture was stirred for 24 h at 1008C. The solvent was evaporated
under reduced pressure and the residue was extracted with n-hexane (2ꢂ
10.0 mL). The extracts were combined and concentrated to about
10.0 mL. Products were obtained by recrystallization from the concen-
trated hexane solution at 08C for several days. Colorless crystals, 79%
yield. M.p. 289–2918C; 1H NMR (300 Hz, C6D6, 258C): d=7.21–7.02 (m,
3H), 6.67–5.25 (m, 3H), 3.85 (d, 2H), 2.43 (s, 6H), 0.34–0.14 ppm (d,
18H); IR (KBr pellet): n˜ = 3587 (w), 3564 (w), 3387 (s), 1558 (w), 1539
(w), 1474 (s), 1435 (w), 1258 (w), 1196 (w), 1096 (s), 1026 (s), 976 (w),
953 (w), 910 (w), 883 (w), 768 (s), 721 (s), 644 (w), 544 cmÀ1 (w); elemen-
tal analysis calcd (%) for C42H72ON6Si4Y2: C 52.21, H 7.41, N 8.70;
found: C 52.28, H 7.36, N 9.02.
General Procedures for hydrophosphonylations of ketones: A 30.0 mL
Schlenk tube was charged under dried argon with the dinuclear rare
earth metal amido complex 2 (17.9 mg, 0.02 mmol) and diethyl phosphite
(3.32 g, 24 mmol), either under solvent-free conditions or in THF
(2.0 mL), and the relevant ketone (20.0 mmol) was then added to the
mixture. The resulting mixture was allowed to stir at RT for 20 min.
After the reaction was complete, the mixture was hydrolyzed with water
(3 mL), extracted with ethyl acetate (3ꢂ10 mL), dried over anhydrous
Na2SO4, and filtered. After the solvent had been removed under reduced
pressure, the final products were further purified by washing with
hexane. The full characterization data for the resulting products can be
found in the Supporting Information.
Synthesis of {(m-h5:h1):h1-2-[(2,6-Me2C6H3)NCH2]
(3): Complex 3 was prepared as pale blue crystals in 71% yield from the
reaction between compound 1 (0.40 g, 2.00 mmol) and [(Me3Si)2N]3Nd(m-
Cl)Li(THF)3 (1.77 g, 2.00 mmol) by procedures similar to those used for
ACHTUTNGRENGU(N C4H3N)NdNACHTUGNTERN(NUGN SiMe3)2}2
AHCTUNGTRENNUNG
ACHTUNGTRENNUNG
the preparation of 2. M.p. 283–2858C; IR (KBr pellet): n˜ = 3352 (m),
3291 (s), 3125 (w), 2943 (m), 1508 (m), 1474 (s), 1447 (m), 1424 (m), 1377
(w), 1339 (m), 1257 (m), 1234 (m), 1196 (s), 1126 (s), 1096 (vs), 1026 (s),
945 (m) ,826 (m), 783 (s), 729 (s), 648 (m), 606 (w), 548 cmÀ1 (w); ele-
mental analysis calcd (%) for C38H64N6Si4Nd2: C 45.38, H 6.41, N 8.36;
found: C 45.65, H 6.31, N 8.42.
Synthesis of {(m-h5:h1):h1--2-[(2,6-Me2C6H3)NCH2]
(4): Complex 4 was prepared as yellow crystals in 83% yield from the re-
action between compound 1 (0.40 g, 2.00 mmol) and [(Me3Si)2N]3Sm(m-
Cl)Li(THF)3 (1.78 g, 2.00 mmol) by procedures similar to those used for
the preparation of 2. M.p. 280–2828C; IR (KBr pellet): n˜ = 3565 (w),
3403 (s), 3102 (w), 3044 (w), 2944 (m), 2855 (w), 1509 (m), 1474 (s), 1435
(w), 1397 (w), 1377 (w), 1339 (w), 1258 (m), 1196 (m), 1096 (s), 1026 (s),
989 (w), 945 (w), 910 (w), 883 (w), 768 s), 721 (s), 652 (w), 544 cmÀ1 (m);
elemental analysis calcd (%) for C38H64N6Si4Sm2: C 44.83, H 6.34, N 8.26;
found: C 44.86, H 6.16, N 8.12.
ACHTUTNGRENGU(N C4H3N)SmNACHTUGNTERN(NUGN SiMe3)2}2
Acknowledgements
AHCTUNGTRENNUNG
ACHTUNGTRENNUNG
Financial support for this work from the National Natural Science Foun-
dation of China (20832001, 20802001, 21072004, 21172003) and the Na-
tional Basic Research Program of China (2012CB821604) and grants
from the Ministry of Education (20103424110001), and Anhui province
(TD200707, 11040606M36) are gratefully acknowledged.
Synthesis of {(m-h5:h1):h1--2-[(2,6-Me3C6H2)NCH3]
ACHTUNRGTENNG(U C4H3N)DyNACHTUGNTERN(NUGN SiMe3)2}2
(5): Complex 5 was prepared as a colorless crystalline solid in 81% yield
from the reaction between compound 1 (0.40 g, 2.00 mmol) and
[1] a) R. L. Hilderbrand, The Role of Phosphonates in Living Systems,
CRC Press, Boca Raton, 1983; b) R. Engel, Handbook of Organo-
phosphorus Chemistry, Marcel Dekker, New York, 1992; c) A. Szy-
[(Me3Si)2N]3DyACHTUNGTRENNUNG(m-Cl)LiACHTUNGTRENNUNG(THF)3 (1.80 g, 2.00 mmol) by procedures similar
´
´
manska, M. Szymczak, J. Boryski, J. Stawinski, A. Kraszewski, G.
Collu, G. Sanna, G. Giliberti, R. Loddo, P. L. Colla, Bioorg. Med.
Chem. 2006, 14, 1924.
to those used for preparation of 2. M.p. 287–2898C; IR (KBr pellet): n˜ =
3352 (m), 2967 (w), 1626 (w), 1591 (w), 1476 (s), 1445 (m), 1422 (m),
1098 (m), 1026 (s), 824 (m), 797 (s), 783 (m), 737 (m), 727 (m), 650 (m),
606 cmÀ1 (m); elemental analysis calcd (%) for C38H64N6Si4Dy2: C 43.79,
H 6.19, N 8.06; found: C 43.98, H 6.04, N 7.63.
Synthesis of {(m-h5:h1):h1-2-[(2,6-Me3C6H3)NCH2]
(6): Complex 6 was prepared as red crystals in 75% yield from the reac-
tion between compound 1 (0.40 g, 2.00 mmol) and [(Me3Si)2N]3Yb(m-
Cl)Li(THF)3 (1.83 g, 2.00 mmol) by procedures similar to those used for
ACHTUTNGRENGU(N C4H3N)YbNACHTUGNTERN(NUGN SiMe3)2}2
[3] a) J. P. Duxbury, A. Cawley, M. Thornton-Pett, L. Wantz, J. N. D.
4403–4406; b) J. P. Duxbury, J. N. D. Warne, R. Mushtaq, C. Ward,
1986; e) X. Zhou, X. Liu, X. Yang, D. Shang, J. Xin, X. Feng,
T. Katsuki, Angew. Chem. 2010, 122, 809–811; Angew. Chem. Int.
Ed. 2010, 49, 797–799.
AHCTUNGTRENNUNG
ACHTUNGTRENNUNG
preparation of 2. M.p. 290–2928C; IR (KBr pellet): n˜ = 3408 (m), 3217
(m), 2972 (w), 1628 (s), 1591 (m), 1474 (s), 1440 (s), 1416 (m), 1377 (m),
1337 (w), 1254 (s), 1191 (m), 1096 (m), 1034 (m), 860 (s), 792 (s), 768 (s),
731 (s), 606 cmÀ1 (m); elemental analysis calcd (%) for C38H64N6Si4Yb2:
C 42.92, H 6.07, N 7.90; found: C 43.38, H 5.83, N 7.88.
Crystal structure determinations: Suitable crystals of complexes 2, 3, 4,
and 6 were each mounted in a sealed capillary. Diffraction was per-
formed with a Bruker SMART CCD area detector diffractometer and
use of graphite-monochromated Mo-Ka radiation (l=0.71073 ꢁ); an em-
pirical absorption correction was applied by use of the SADABS pro-
gram.[18] All structures were solved by direct methods, completed by sub-
2658
ꢀ 2012 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
Chem. Eur. J. 2012, 18, 2653 – 2659