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T. Reznícek et al. / Journal of Organometallic Chemistry 718 (2012) 38e42
41
by standard methods, distilled prior to use. The 1H, 13C{1H}, 31P{1H}
4.5. Synthesis of {[2,6-(tBuOCH2)2C6H3]Ph2PNH}Cy3SnCl (5)
and 119Sn{1H} NMR spectra were recorded on a Bruker Avance 400
spectrometerat300KinC6D6 orCDCl3. The1H,13C, 31Pand119SnNMR
0.36 mL (0.57 mmol) of n-BuLi was added drop-wise to the
toluene solution (10 mL) of 3 (0.28 g, 0.57 mmol) at ꢀ78 ꢁC and
resulting dark red solution was stirred for 30 min at ꢀ78 ꢁC. The
Cy3SnCl (0.23 g, 0.57 mmol) was added in one portion and reaction
mixture was stirred for additional 17 h at r.t. Solid was filtered off
and solvent was evaporated and resulting light yellow oil was
washed with hexane (6 mL) to give colourless solid of 5 (yield
0.44 g, 92%). For 5: mp 125e127 ꢁC; Anal. Calcd for C31H45ClNO2PSn
(853.18 g/mol): C, 64.59; H, 8.22. Found: C, 64.68; H, 8.26. 1H NMR
chemical shifts d are given in ppm and referenced to internal Me4Si
(1H and 13C) and external H3PO4 (31P) and Me4Sn (119Sn). Elemental
analyses were performed on an LECO-CHNS-932 analyzer.
4.2. Synthesis of [2,6-(tBuOCH2)2C6H3]Ph2PNSiMe3 (2)
0.11 mL of Me3SiN3 (0.85 mmol) was added to toluene solution
(10 mL) of 1 (0.24 g; 0.56 mmol) and reaction mixture was heated to
85 ꢁC. The reaction was monitored by 31P NMR spectroscopy and
the reaction was complete in 7 days. The solvent was evaporated in
reduced pressure to form orange viscous oil of 2 (yield 0.61 g; 97%).
For 2: Anal. Calcd for C31H44NO2PSi (521.74 g/mol): C, 71.36; H, 8.50.
(C6D6, 400 MHz):
d
0.97 (s, 18H, OtBu); 1.32 (bs, 4H, CyH); 1.69 (bs,
2H, CyH); 1.85 (bs, 4H, CyH); 2.05 (bs, 1H, CyH); 4.28 (d, 1H, PNH)
(2J(1H,31P) ¼ 100 Hz); 4.50 (s, 4H, CH2O); 7.04e7.91 (m, 13H, ArH);
13C NMR (C6D6, 100 MHz):
d 27.2 (CH3); 28.9 (C(1)-Cy;
Found: C, 71.29; H, 8.39. 1H NMR (C6D6, 400 MHz):
SiMe3); 1.04 (s, 18H, OtBu); 4.36 (s, 4H, CH2O); 7.07e8.01 (m, 13H,
d
0.35 (s, 9H,
1J(13C,119Sn) ¼ 560 Hz); 31.2 (C(2,6)-Cy; 2J(13C,119Sn) ¼ 17.0 Hz);
32.4 C(3,5)-Cy; 34.8 C(4)-Cy; 63.4 (CH2O, 3J(13C,31P) ¼ 5 Hz); 72.9
ArH); 13C NMR (C6D6, 100 MHz)
d
(ppm): 2.1 (SiMe3); 27.9 (CH3);
(OCMe3); 126.5 (C(10), 1J(13C,31P)
¼
95 Hz); 127.0 (C(20,60),
63.5 (CH2O, 3J(13C,31P) ¼ 27 Hz); 73.3 (OCMe3); 127.8 (C(30,50),
3J(13C,31P) ¼ 11 Hz); 128.9 (C(3,5), 3J(13C,31P) ¼ 23 Hz); 129.6 C(40);
130.7 C(4); 131.3 (C(20,60), 2J(13C,31P) ¼ 22 Hz); 136.2 (C(10),
1J(13C,31P) ¼ 32 Hz); 140.5 (C(1), 1J(13C,31P) ¼ 100 Hz); 144.5 (C(2,6),
2J(13C,31P) ¼ 10 Hz); 128.1 C(40); 128.3 (C(30,50), 3J(13C,31P) ¼ 12 Hz);
128.9 C(4); 131.5 (C(3,5), 3J(13C,31P)
¼
10 Hz); 135.8 (C(1),
1J(13C,31P) ¼ 100 Hz); 145.1 (C(2,6), 2J(13C,31P) ¼ 13 Hz); 31P NMR
(C6D6, 162 MHz):
186 MHz): d 35.5 (bs).
d
28.0 (2J(31P, 119Sn) ¼ 100 Hz); 119Sn NMR (C6D6,
2J(13C,31P) ¼ 13 Hz); 31P NMR (C6D6, 162 MHz):
29Si) ¼ 104 Hz).
d
ꢀ7.4 (2J(31P,
4.6. Crystallography
4.3. Synthesis of {[2,6-(tBuOCH2)2C6H3]Ph2PNH2}þNꢀ3 (3)
Compounds 3 and 4 were dissolved in toluene/hexane solution,
put to the freezer and let to crystallize at 4 ꢁC. The obtained
materials were suitable for X-ray analysis and characterized as
compounds 3 and 4.
The X-ray data (Table S1) for colourless crystals of 3 and 4 were
obtained at 150 K using Oxford Cryostream low-temperature
0.52 g (1.05 mmol) of 2 was dissolved in toluene (10 mL),
Me3SiN3 (0.27 mL, 2.10 mmol) and distilled water (0.04 mL,
2.1 mmol) were added via syringe. Reaction mixture was stirred for
3 days. The solvent was evaporated and resulting orange oil was
washed with hexane (6 mL) to give light orange solid of 3 (yield
0.49 g, 95%). For 3: mp 127.8e129.7 ꢁC; Anal. Calcd for C28H37N4O2P
(492.59 g/mol): C, 68.12; H, 7.76. Found: C, 68.08; H, 7.70. 1H NMR
device on a Nonius KappaCCD diffractometer with MoKa radiation
ꢁ
(l
¼ 0.71073 A), a graphite monochromator, and the
f and c scan
(C6D6, 400 MHz):
d
0.97 (s, 18H, OtBu); 4.35 (s, 4H, CH2O); 7.10e7.85
27.0
mode. Data reductions were performed with DENZO-SMN [17]. The
absorption was corrected by integration methods [18]. Structures
were solved by direct methods (Sir92) [19] and refined by full
matrix least-square based on F2 (SHELXL97) [20]. Hydrogen atoms
were mostly localized on a difference Fourier map, however to
ensure uniformity of the treatment of the crystal, all hydrogen
atoms were recalculated into idealized positions (riding model) and
assigned temperature factors Hiso(H) ¼ 1.2 Ueq(pivot atom) or of
(m, 13H, ArH); 8.00 (bs, 2H, NH2); 13C NMR (CDCl3, 90 MHz):
d
(CH3); 59.6 (CH2O, 3J(13C,31P) ¼ 5 Hz); 73.2 (OCMe3); 120.6 (C(10);
1J(13C,31P) ¼ 90 Hz]; 125.4 C(40); 126.5 C(4); 129.4 (C(30,50),
3J(13C,31P) ¼ 14 Hz); 129.8 (C(20,60), 2J(13C,31P) ¼ 11 Hz); 132.5
(C(3,5), 3J(13C,31P) ¼ 12 Hz); 135.3 (C(1), 1J(13C,31P) ¼ 99 Hz); 145.5
(C(2,6); 2J(13C,31P) ¼ 11 Hz); 31P NMR (CDCl3, 162 MHz):
ESIþ: m/z 450 [M ꢀ N3]þ (100%).
d 30.5; MS:
ꢁ
1.5 Ueq for the methyl moiety with CeH ¼ 0.96, 0.97, and 0.93 A for
4.4. Synthesis of {[2,6-(tBuOCH2)2C6H3]Ph2PNH}Me3SnCl (4)
methyl, methylene and hydrogen atoms in aromatic rings, respec-
ꢁ
tively, and 0.97 A for NeH groups.
0.29 mL (0.46 mmol) of n-BuLi was added drop-wise to the
toluene solution (10 mL) of 3 (0.22 g, 0.46 mmol) at ꢀ78 ꢁC and
resulting dark red solution was stirred for 30 min at ꢀ78 ꢁC. The
Me3SnCl (0.09 g, 0.46 mmol) was added at one portion and reaction
mixture was stirred for additional 17 h at r.t. Solid was filtered off
and solvent was evaporated and resulting light yellow oil was
washed with hexane (6 mL) to give colourless solid of 4 (yield
0.49 g, 90%). For 4: mp 125e127 ꢁC; Anal. Calcd for C31H45ClNO2PSn
(648.83 g/mol): C, 57.39; H, 6.99. Found: C, 58.08; H, 7.15. 1H NMR
Acknowledgement
The authors wish to thank the Grant Agency of the Czech
Republic (project no. P207/10/0215) and The Ministry of Education
of the Czech Republic for financial support.
Appendix A. Supplementary material
(C6D6, 400 MHz):
d
0.60 (s, 9H, Me3Sn, 2J(119Sn,1H) ¼ 68.5 Hz); 0.94
(s, 18H, OtBu); 4.19 (d, 1H, PNH, 2J(1H,31P) ¼ 101 Hz); 4.48 (s, 4H,
CCDC 882967 and 882968 contain the supplementary crystal-
lographic data for this paper. These data can be obtained free of
charge from The Cambridge Crystallographic Data Centre via www.
CH2O); 6.94e7.65 (m, 13H, ArH); 13C NMR (C6D6, 125 MHz):
d 1.1
(SnCH3; 1J(13C,119Sn)
¼
558 Hz); 27.4 (CH3); 63.5 (CH2O;
3J(13C,31P) ¼ 5 Hz); 73.0 (OCMe3); 126.1 (C(10), 1J(13C,31P) ¼ 100 Hz);
127.2 (C(30,50), 3J(13C,31P) ¼ 11 Hz); 128.4 C(40); 128.7 (C(3,5),
3J(13C,31P) ¼ 11 Hz); 131.4 C(4); 131.4 (C(20,60), 2J(13C,31P) ¼ 20 Hz);
135.6 (C(1); 1J(13C,31P) ¼ 100 Hz); 145.3 (C(2,6); 2J(13C,31P) ¼ 21 Hz);
Appendix B. Supplementary material
31P NMR (C6D6,162 MHz):
d
28.9 (2J(31P, 119Sn) ¼ 113 Hz); 119Sn NMR
(C6D6, 186 MHz):
(100%).
d
24.7 (bs); MS: ESIþ: m/z 450 [M-Me3SnCl þ H]þ
Supplementary material related to this article can be found at