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Dalton Transactions
Page 8 of 11
DOI: 10.1039/C5DT04612B
ARTICLE
Journal Name
1H NMR (300 MHz, THF-d8, 25 °C):
δ 8.62 (s, 1H, H7), 8.56 (s, solution, a Pinacolborane-precursor-solution and the catalyst-
1H, H14), 8.00-7.94 (m, 2H, H6+H12), 7.92 (d, 1H, JH3- solution, were put into a screw-cap-flask, treated with 2 mL of
4
H5=1.6 Hz, H5), 7.53 (dd, 3JH3-H2=8.7 Hz, JH3-H5=1.7 Hz, H3), 7.37 a 2M solution of potassium-carbonate in water and stirred at
4
3
(s, 1H, H16), 7.35 (dd, 1H, JH18-H19=9.8 Hz, JH16-H18=2.6 Hz, 70 °C for 24 h. Thereafter, the solvent was removed in vacuo,
4
3
H18), 7.24-7.17 (m, 2H, H10+H11), 6.85 (d, 1H, JH18-H19=9.1Hz, the residue suspended in methanol, filtered off, washed with
H19), 6.84 (d, 1H, 3JH2-H3=8.7Hz, H2), 1.31 (s, 12H, H24), 1.29 water, methanol and diethyl-ether and dried in vacuo. The
(s, 9H, H22).
raw-product was then dissolved in pyridine, filtered over celite
and crystallized by addition of n-hexane. Yields:
4+
6: 95 mg,
13C NMR (75 MHz, THF-d8, 25 °C): δ 169.8 (C1), 166.4 (C20), 0.11 mmol, 56 %;
156.2 (C7), 155.8 (C14), 144.3 (C8 C13), 143.7 (C5), 140.6 (C3), 0.13 mmol, 66 %;
137.8 (C17), 134.1 (C18), 129.1 (C16), 127.8+127.5 (C10
121.5+121.1 (C2 C19), 120.2 (C15), 116.1+116.0 (C9
83.9 (C23), 34.5 (C21), 34.1 (C24), 25.1 (C22).
4
+
7: 121 mg, 0.13 mmol, 66 %;
5+6: 119 mg,
+
5+7: 177 mg, 0.183 mmol 93 %.
+
C11), Due to very low solubility of all four coupling-products, only
C12), 1H-NMR-spectra could be obtained.
+
+
8
:
MS (FAB+,HRMS) m/z 555.1983 [M+H]+ (calculated: 555.1965).
1H NMR (300 MHz, DMSO-d6, 25 °C):
δ
8.11-8.05 (m, 4H), 7.83 (d, JH-H=2.5 Hz, 2H), 7.64 (dd, JH-
8.84 (s, 2H), 8.76 (s, 2H),
3
4
4
4
Elemental analysis: found: C 64.8, H 6.00, N 5.01, O 11.3 H=9.0 Hz, JH-H=2.6 Hz, 2H), 7.55 (d, JH-H=2.6 Hz, 2H), 7.43 (dd,
4
3
(calculated: C 64.9, H 5.99, N 5.05, O 11.5).
3JH-H=8.9 Hz, JH-H=2.7 Hz), 7.34-7.31 (m, 4H), 7.00 (d, JH-
H=8.9 Hz), 6.88 (d, 3JH-H=9.0 Hz), 1.34 (s, 18H).
Synthesis of N-(3,5-di-tert-butylsalicylidene)-N'-(5-
(4,4,5,5,-tetramethyl-1,3,2-dioxa-borolan-2-
yl)salicylidene)phenylenediaminato nickel(II) (7).
MS(MALDI+,DHB) m/z 911.3 [M+H]+ (calculated: 911.3), 933.3
[M+Na]+ (calculated: 933.2), 949.3 [M+K]+ (calculated: 949.2).
Simulated isotope patterns match, see Fig. S15.
This substance was synthesized according to the general
procedure for the preparation of salophenato-nickel(II)-
Elemental analysis: found: C 67.0, H 5.04, N 6.44, O 7.66
(calculated: C 67.3, H 4.94, N 6.54, O 7.47).
complexes (v.s.). Monoimine
2:
513 mg, 1.58 mmol,
nickelacetate-tetrahydrate:
398 mg, 1.60 mmol,
9,10
:
salicylaldehyde
mmol, 99.8 %.
3: 383 mg, 1.31 mmol. Yield: 695 mg, 1.31
1H NMR (300 MHz, THF-d8, 25 °C):
δ 8.68 (s, 1H), 8.61 (s, 1H),
8.49 (s, 1H), 8.47 (s, 1H), 8.03-7.97 (m, 2H), 7.93-7.89 (m, 2H),
4
7.61-7.50 (m, 4H), 7.40 (d, JH-H=2.5 Hz), 7.38-7.33 (m, 2H),
1H NMR (300 MHz, THF-d8, 25 °C):
δ 8.67 (s, 1H, H7), 8.52 (s,
1H, H14), 7.95 (d, 1H, JH3-H5=2.0 Hz, H5), 8.00-7.94 (m, 3H,
3
3
4
7.23-7.16 (m, 6H), 6.98 (d, JH-H=8.9 Hz), 6.91 (d, JH-H=8.9 Hz),
6.86 (d, 3JH-H=8.8 Hz), 1.49 (s, 9H), 1.32 (s, 9H), 1.31 (s, 9H).
MS(MALDI+,DHB) m/z 911.3 [M+H]+ (calculated: 911.3), 933.3
[M+Na]+ (calculated: 933.2), 949.3 [M+K]+ (calculated: 949.2).
Simulated isotope patterns match, see Fig. S 15.
3
4
H9+H12), 7.55 (dd, 1H, JH2-H3=8.7 Hz, JH3-H5=1.8 Hz, C3), 7.39
(d, 1H, 4JH16-H18=2.6 Hz, H18), 7.23 (d, 1H, 4JH16-H18=2.6 Hz, H16),
3
7.26-7.20 (m, 2H, H10+H11), 6.84 (d, 1H, JH2-H3=8.7 Hz, H2),
1.46 (s, 9H, H24), 1.30-1.32 (m, 21H, H22, H26),
Elemental analysis: found: C 67.4, H 5.59, N 6.11 (calculated: C
68.5, H 5.52, N 6.14).
13C NMR (75 MHz, THF-D8, 25 °C):
δ 170.2 (C1), 165.6 (C20),
156.0 (C7), 155.8 (C14), 144.5 (C13), 144.0 (C8), 143.7 (C5),
141.3 (C19), 140.3 (C3),137.2 (C17), 130.5 (C18), 127.8 (C16),
127.3 + 127.2 (C10+C11), 122.0 (C4), 121.6 (C6), 121.4 (C2),
120.7 (C15), 115.9 + 115.7 (C9+C12), 83.7 (C25), 36.3 (C23),
34.7 (C21), 31.5 (C24), 29.8 (C26), 25.1 (C22).
11
:
1H NMR (300 MHz, THF-d8, 25 °C):
δ
8.71 (s, 2H), 8.55 (s, 2H),
8.03-7.95 (m, 4H), 7.67 (s, 2H), 7.63-7.59 (m, 2H), 7.40 (s, 2H),
7.25-7.22 (m, 6H), 6.99-6.96 (m, 2H), 1.48 (s, 18H), 1.32 (s,
18H).
MS(MALDI+,DHB) m/z 966.4 [M]+ (calculated: 966.3), 989.3
[M+Na]+ (calculated: 989.3). Simulated isotope patterns
match, see Fig. S 15.
MS (FAB+,HRMS) m/z 611.2582 [M]+ (calculated: 611.2591).
Elemental analysis: found: C 66.81, H 6.76, N 4.58, O 10.5
(calculated: C 67.09, H 6.83, N 4.65, O 10.1).
Elemental analysis: found: C 69.2, H 6.00, N 5.66, O 6.72
(calculated: C 69.5, H 6.04, N 5.79, O 6.61).
Procedure for the Suzuki-Miyaura-cross-coupling:
Computational Details
Stock-solutions of the four precursors were prepared, each in
DFT-calculations were performed using the Gaussian09
software-package[46] with the B3-LYP hybrid-functional and
def2-TZVP basis for all atoms.[47] The geometries were
optimized using crystal structural data as starting-values,
where available. To evaluate whether the optimized
geometries are indeed the global energy-minimum, frequency
15 mL of absolute THF:
4
: 306 mg, 0.602 mmol,
5
: 334 mg,
0.592 mmol,
0.599 mmol.
6
:
330 mg, 0.595 mmol and
7
:
366 mg,
A
stock-solution of the catalyst Pd(PPh3)4
(310 mg, 0.268 mmol in 25 mL of THF) was also prepared. For
the four coupling-reactions, 5 mL each of a Br-precursor-
8 | J. Name., 2012, 00, 1-3
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