27.73 (s, 2C, C6H3(CHMe2)2), 24.75 (s, 1C, NCCH3), 23.69 (s, 2C,
C6H3(CH(CH3)2)2), 23.31 (s, 2C, C6H3(CH(CH3)2)2), 21.75 (s, 2C,
C6H3(CH3)2) ppm. 31P NMR (400 MHz, C6D6, 25 ◦C, H3PO4 was
used as standard): d -3.55, -15.48 ppm. Anal. Calcd for C35H41N2P
(%): C, 80.73; H, 7.94; N, 5.38. Found: C, 80.94; H, 7.97; N, 5.36%.
9 Selected NMR data for 2 LSc(CH2SiMe3)2: 1H NMR (600 MHZ, C6D6,
25 ◦C): d 7.66 (br, 4H, o-PPh2), 3.64 (m, 2H, 3JH–H = 6.6 Hz CH(CH3)2),
3.21 (d, 1H, 2JP–H = 12.0 Hz, CHPPh2), 2.04 (s, 6H, C6H3(CH3)2), 1.87
Acknowledgements
This work was financially supported by the financial supports from
the National Natural Science Foundation of China (No. 20934006)
and the MST of China (Nos. 2009AA03Z501 and 51021003).
Notes and references
3
(s, 3H, CCH3), 1.42 (d, 6H, JH–H = 6.0 Hz, CH(CH3)2), 1.38 (d, 6H,
2
3JH–H = 6.0 Hz, CH(CH3)2), 0.51 and 0.32 (AB, 4H, JH–H = 10.8 Hz,
‡ Crystallographic data for 2: C43H62N2PScSi2, M = 739.06, monoclinic,
1
CH2SiMe3), 0.31 (s, 18H, Si(CH3)3) ppm. 13C { H} NMR (150 MHz,
˚
˚
˚
space group P21/c, a = 12.2513(7) A,◦b = 21.0117(12) A, c = 17.6635(10)
C6D6, 25 ◦C):d 175.04 (s, 1C, NC), 55.27 (d, JP–C = 127.5 Hz, 1C,
CHP), 44.31 (s, 1C, CH2SiMe3), 28.79 (s, 2C, CH(CH3)2), 25.60 (s, 4C,
CH(CH3)2), 25.31 (s, 1C, CCH3), 21.11 (s, 2C, C6H3(CH3)2), 3.68 (s,
1C, Si(CH3)3) ppm. 31P NMR (400 MHZ, C6D6, 25 ◦C, H3PO4 was used
as standard)d 16.0 ppm. Anal. Calcd for C43H62N2PScSi2 (%) C, 69.88;
H, 8.46; N, 3.79. Found: C, 70.03; H, 8.48; N, 3.78.
◦
◦
A, a = 90 , b = 107.6920(10) , g = 90 , V = 4331.9(4) A , t = -88 ◦C, Z =
4, Dc = 1.133 g cm-3, m = 2.92 cm-1, Rint = 0.0271, GOF = 1.037, R = 0.0438,
Rw = 0.1064, R (all data) = 0.0543, Rw (all data) = 0.1135, no. of reflections
collected = 24125, no. of unique reflections = 8515. CCDC 780645.
3
˚
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12 [Ph3C][B(C6F5)4] (4.8 mg, 5.0 mmol) was dissolved in C6D6 (0.5 mL)
and the resulting yellow solution was added to solution of 2 (3.8 mg,
5.0 mmol). The orange solution was formed and added to an NMR
tube, sealed, and analyzed in situ. Selected 1H NMR data for 3
[LScCH2SiMe3][B(C6F5)4]: 1H NMR (300 MHZ, C6D6, 25 ◦C): d 7.64
3
(br, 4H, o-PPh2), 3.63 (m, 2H, JH–H = 6.9 Hz CH(CH3)2), 3.19 (br,
1H, CHPPh2), 2.03 (br, 6H, C6H3(CH3)2), 1.84 (br, 3H, CCH3), 1.39
(quart, 12H, 3JH–H = 6.0 Hz, CH(CH3)2), 0.51 (br, 2H, CH2SiMe3), 0.31
(br, 9H, Si(CH3)3) ppm. The 11B NMR data for compound 3 and trityl
borate were detected by Bruker AV300 spectrometer and BF3·Et2O was
used as external standard (0.00 ppm) in C6D6. The signal of 3 was at
d -16.62 ppm which changed little compared with that of trityl borate
(d -16.80 ppm). The 19F NMR data for compound 3 and trityl borate
were detected by Bruker AV300 spectrometer and BF3·Et2O was used
as external standard (0.00 ppm) in C6D6. The signals of 3 were at d
-56.01, -86.64 and -90.47 ppm which changed little compared with
that of trityl borate (d -56.16, -86.60 and -90.56 ppm). The 31P NMR
datum of 3 (d 21.13 ppm) was detected by Bruker AV400 spectrometer
and H3PO4 was used as external standard (0.00 ppm) in C6D6.
13 The formation of Ph3CCH2SiMe3 was confirmed by the 1H NMR
spectrum of a sample prepared from Ph3CCl and LiCH2SiMe3 in
C6D6. Ph3CCl (1.4 mg, 5.0mmol) was dissolved in C6D6 (0.5 mL) and
the resulting yellow solution was added to solid LiCH2SiMe3 (0.5 mg,
5.0mmol). The light orange solution was added to an NMR tube, sealed,
and analyzed in situ by Bruker AV300 spectrometer.
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(b) Selected NMR data for 1: 1H NMR (300 MHz, CDCl3, 25 ◦C,
major isomer 1a): d 7.85 (m, 4H, o-PPh2), 3.77 (d, 2JP–H = 14.0 Hz, 2H,
PCH2), 2.78 (m, 2H, C6H3(CHMe2)2), 2.51 (s, 6H, C6H3(CH3)2), 1.62
(s, 3H, NCCH3), 1.16 (quart, 3JH–H = 7.0 Hz, 12H, C6H3(CH(CH3)2)2).
13C { H} NMR (75 MHz, CDCl3, 25 ◦C, major isomer 1a):d 165.30
1
2
(d, JP–C = 6.0 Hz, 1C, NC), 45.62 (d, JP–C = 60.0 Hz, 1C, PCH2),
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The Royal Society of Chemistry 2011
Dalton Trans., 2011, 40, 2151–2153 | 2153
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