Si(CH
3
)
3
{free}), 1.15 (d, 12 H, CH
3
{DippNNN(H)Dipp}),1.19 (d, 12 H,
9
1
M. Haehnel, M. Ruhmann, O. Theilmann, S. Roy, T. Beweries, P. Arndt,
A. Spannenberg, A. Villinger, E. D. Jemmis, A. Schulz, U. Rosenthal, J.
Am. Chem. Soc. 2012, 134, 15979–15991.
CH {DippNH
3
2
}), 6.43 (10 H, CH{Cp Ti}).
2
0
K. Kaleta, M. Ruhmann, O. Theilmann, S. Roy, T. Beweries, P. Arndt, A.
Villinger, E. D. Jemmis, A. Schulz, U. Rosenthal, Eur. J. Inorg. Chem.
Compound 2TerTol: To a stirred solution of TerNNN(H)m-Tol (200 mg,
.44 mmol) in benzene (6 mL), a solution of [Cp TiCl] (88 mg, 0.22 mmol)
0
2
2
2
012, 4, 611–617.
A. Hinz, R. Kuzora, U. Rosenthal, A. Schulz, A. Villinger, Chem. Eur. J.
014, 20, 14659–14673.
in benzene (6 mL) is added. The dark yellow solution is stirred overnight
turning brown. Subsequently, the solvent is removed in vacuo and the solid
residue is dissolved in THF (2 mL). The solution is concentrated and stored
at 5 °C, resulting in formation of small yellow needle-shaped crystals of
11
12
13
2
M. Haehnel, S. Hansen, A. Spannenberg, P. Arndt, T. Beweries, U.
Rosenthal, Chem. Eur. J. 2012, 18, 10546-10553.
2TerTol (204 mg, 0.33 mmol, 73 %). Mp: 166 °C. EA for C41
42 3
H N Ti found
W. W. Hartman, J. B. Dickey, Org. Synth. 1934, 14, 24–26.
a) N. Nimitsiriwat, V. C. Gibson, E. L. Marshall, P. Takolpuckdee, A. K.
Tomov, A. J. P. White, D. J. Williams, M. R. J. Elsegood, S. H. Dale,
(calc.): C 78.60 (78.83), H 6.54 (6.78), N 6.38 (6.73). IR (ATR, 25°C, 16
-
1
14
scans cm ):2968 (w), 2945 (w), 2912 (w), 2855 (w), 1597 (m), 1583 (w),
1
1
481 (w), 1441 (w), 1404 (w), 1372 (w), 1332 (w), 1307, (w), 1243 (s),
231 (s), 1185 (m), 1158 (s), 1125 (m), 1088 (m), 1066 (m), 1014 (m), 983
Inorg. Chem. 2007, 46, 9988–9997; b) A. G. M. Barrett, M.
R.
Crimmin, M. S. Hill, P. B. Hitchcock, G. Kociok-Köhn, P. A. Procopiou,
Inorg. Chem. 2008, 16, 7366–7376.
(
7
(
m), 905 (w), 895 (w), 872 (w), 862 (w), 849 (m) 814 (m), 804 (m), 781 (s),
59 (s), 742 (m), 694 (m), 678 (m), 663 (m), 616 (w), 604 (w), 592 (m), 573
w), 557 (w), 542 (m), 517 (w), 507 (m), 478 (w), 447 (w), 429 (m), 404 (w).
1
5
S. G. Alexander, M. L. Cole, C. M. Forsyth, S. K. Furfari, K. Konstas,
Dalton Trans. 2009, 13, 2326–2336.
-
1
Raman (632 nm, cm ): 995 (1), 1246 (2), 1288 (2), 1332 (10), 1403 (3),
1
Ter/m-Tol]+.
16
a) H. S: Lee, M. Niemeyer, Inorg. Chem. 2006, 45, 6126–6128; b) H. Lee,
S. Hauber, D. Vinduꢀ, M. Niemeyer, Inorg. Chem. 2008, 47, 4401–4412;
c) H. Lee, M. Niemeyer, Inorg. Chem. 2010, 49, 730–735; d) S.-O.
Hauber, F. Lissner, G. B. Deacon, M. Niemeyer, Angew. Chem. Int. Ed.
582 (2), 1597 (1). MS (CI, pos., m/z (%): 624 (100) [Cp TiN
2 3
Compound 3: A solution of 2Ph (0.103 g, 0.28 mmol) in benzene (5 mL)
is added to a solution of Ag[CHB11 Br ] (0.200 g, 0.28 mmol) in benzene
10 mL). The solution turns immediately dark red and a black precipitate is
H
5
6
2005, 44, 5871–5875; e) S. Balireddi, M. Niemeyer, Acta Cryst., Sect. E:
(
Struct. Rep. Online 2007, 63, o3525.
formed. The suspension is stirred for one hour at room temperature and
subsequently filtered. After removal of the solvent in vacuo the red solid is
dissolved in toluene (8 mL). The dark red brown suspension is filtered; the
solution is concentrated and stored at 5 °C, resulting in formation of small
red crystals of 3, which are suitable for structural analysis (38 mg, 204 mg,
17
A. Hinz, A. Schulz, A. Villinger, J.-M. Wolter, J. Am. Chem. Soc. 2015,
137, 3975–3980.
18
19
20
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0
.05 mmol, 17 %). 1H NMR (25 °C, [D8]THF, 300.13 MHz): 0.63-3.43 (m,
vb [CHB11
(
−
H
5
Br
6
]), 7.02-7.64 (m, 9H, CH), 8.29 (b, 3H, NH); 11B NMR
2
22
25 °C, [D8]THF, 96.29 MHz): −22.09 (d, B7−11, J(11B1H) = 163 Hz),
11.54 (b, B2-6), −3.59 (b, B1).
23
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for this paper. These data can be obtained free of charge from The
Cambridge Crystallographic Data Centre.
2
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Keywords: Titanium • Triazenides • N Ligands • Triazenes •
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