Journal of Inorganic and General Chemistry
ARTICLE
Zeitschrift für anorganische und allgemeine Chemie
(
400.1 MHz, CDCl
3
): δ = 7.71 (d, 3JHH = 8.0 Hz, 2 H, H2), 7.64 (dd, 3009w, 2958m, 2875w, 1603m, 1575m, 1497m, 1452s, 1391w, 1346m,
3
3
3
J
HH = 8.0, JHH = 8.0 Hz, 1 H, H1), 3.89 (s, 6 H, H15), 3.28 (d, JHH
4.0 Hz, 2 H, H10), 2.13–2.08 (m, 2 H, H9eq), 1.85–1.82 (m, 2 H,
1318w, 1290w, 1271w, 1251w, 1227w, 1206w, 1163m, 1125vs, 1075m,
1054m, 1029w, 1015w, 919w, 827w, 814s, 780w, 765w, 734vs, 723s,
701s, 692s, 669m cm .
=
–
1
H8eq), 1.37 (s, 6 H, H11), 1.33–1.27 (m, 4 H, H8ax, H9ax), 0.94 (s, 6
H, H14), 0.80 (s, 6 H, H13). C NMR (100.6 MHz, CDCl
1
13
3
): δ =
[
2,6-Bis(N-methyl-(1R,4R)-1,7,7-trimethylbicyclo[2.2.1]heptanyl-
55.5 (C1), 152.7 (C4), 143.9 (C6), 136.8 (C3), 128.3 (C5), 118.1
pyrazol-3-yl)pyridine]diacetatoiron(II) (5a): 62.3 mg (0.36 mmol)
(
(
C2), 62.7 (C7), 52.7 (C12), 48.8 (C10), 37.3 (C15), 33.8 (C8), 27.5
of colorless iron(II) acetate were dissolved in 12 mL of dry thf and
C9), 20.6 (C14), 19.8 (C13), 11.4 (C11). IR (ATR): ν˜ = 2979m,
179 mg of (0.39 mmol) of ligand 3a were added. The pale yellow reac-
2
1
9
952m, 2870m, 1599w, 1571vs, 1529m, 1472w, 1455m, 1428s,
409m, 1387m, 1222w, 1147w, 1131w, 1106m, 1056w, 1019m, 1001w,
tion mixture was stirred for 72 h at room temperature, while it trans-
formed into an deep red solution. Afterwards the solvent was removed
under reduced pressure, the dark red solid was washed twice with 5 mL
of degassed n-pentane and dried under reduced pressure. Yield:
–
1
30w, 919w, 827vs, 822vs, 778w, 750m, 724w, 691w, 662m cm .
): m/z calcd. 455.3049; found: 455.3062.
37 5
HR-GC-MS (C29H N
2
,6-Bis(N-benzyl-(1R,4R)-1,7,7-trimethylbicyclo[2.2.1]heptanyl- 150 mg (67%). C33
5 4
H43FeN O : calcd. C 62.96, H 6.88, N 11.12%;
pyrazol-3-yl)pyridine (3b): 240 mg (10 mmol) of NaH were sus- found C 62.59, H 7.15, N 11.17%. IR (ATR): ν˜ = 2953m, 2869w,
pended in 50 mL of dry thf. 1.71 g (4.00 mmol) of compound 2 were 1570vs, 1452vs, 1429vs, 1413vs, 1388vs, 1376vs, 1367vs, 1314m,
added and the reaction mixture was stirred for 18 h at room temp. 1271s, 1247m, 1156m, 1125m, 1047m, 1011m, 931w, 921w, 819s,
–
1
3 +
During this time the color of the mixture changed to dark red. 1.75 g
10 mmol) of benzylic bromide were added and the mixture was heated
to reflux for 24 h. Then the solvent was removed and the residue was
treated with 30 mL of CH Cl . The mixture was washed twice with
5 mL of water and the organic phase was dried with MgSO . Re-
778w, 743m, 675w cm . ESI-MS: m/z calcd. for [M-OOCCH ]
570.25, found: 570.00.
(
Catalytic Reactions: All catalytic experiments were performed in
crimp top vials purchased from VWR International GmbH with a total
volume of 20 mL. Acetophenone, catalysts and bases were weighed
and filled in the vials, a magnetic stirring bar was added and the vials
were sealed with ptfe septa. Fluid components and substrates were
added by Hamilton® syringes. The vials were placed in a preheated
aluminum heating block with normed boreholes. Samples of 0.1 mL
were taken with single use syringes and cannula (Braun GmbH). The
samples were filtered through a short column filled with small amounts
of neutral aluminum oxide and MgSO and eluted with ethyl acetate.
The samples were analyzed using a Clarus 580 GC equipped with a
FID-detector or a Varian 3900 GC-MS (2100T). GC columns: FS-
OV-1701-CB-0.25 (30 m, d = 0.25 mm, CS Chromatographie Service
GmbH). Helium (60 kPa) was used as the carrier gas. The injector
temperature was set to 250 °C with a split-value of 25:8 and an oven
2
2
1
4
moval of the solvent resulted in a yellow, highly viscous foam. The
raw product was recrystallized from n-hexane to give colorless crys-
tals. Yield: 1.74 g (71 %). C41
H
47
N
5
6 14
·(C H )0.5 (625.95): calcd. C
1
80.94, H 8.34, N 10.73%; found C 81.02, H 7.90, N 10.54%.
H
3
NMR (400.1 MHz, CDCl
3
): δ = 7.84 (d, JHH = 8.0 Hz, 2 H, H2), 7.68
3
(
5
t,
J
HH = 8.0 Hz, 1 H, H1), 7.30–7.11 (m, 10 H, H17, H18, H19),
2
2
.42 (d, JHH = 16.0 Hz, 2 H, H15), 5.33 (d, JHH = 16.0 Hz, 2 H,
3
H15), 3.32 (d, JHH = 4.0 Hz, 2 H, H10), 2.11–2.02 (m, 2 H, H9eq),
.72–1.68 (m, 2 H, H8eq), 1.38–1.32 (m, 2 H, H8ax), 1.16 (s, 6 H,
H11), 1.12–1.05 (m, 2 H, H9ax), 0.88 (s, 6 H, H14), 0.77 (s, 6 H, H13).
4
1
1
3
C NMR (100.6 MHz, CDCl
C6), 138.2 (C16), 136.8 (C1), 129.2 (C5), 128.7 (C19), 127.6 (C17),
26.7 (C18), 118.3 (C2), 62.9 (C7), 54.3 (C15), 52.8 (C12), 48.9
C10), 33.5 (C8), 27.5 (C9), 20.6 (C14), 19.8 (C13), 11.4 (C11) ppm.
IR (ATR): ν˜ = 3056w, 2955s, 2870m, 1597w, 1569vs, 1539w, 1524m,
497m, 1420vs, 1387m, 1365w, 1312w, 1285m, 1272m, 1254w,
189w, 1178w, 1148w, 1120m, 1088s, 1077s, 1060m, 1030w, 1004m,
3
): δ = 155.3 (C3), 152.9 (C4), 144.3
(
1
(
–
1
temperature heating rate of 6 K·min starting from 80 °C and ending
after 30 min at 260 °C.
1
X-ray Structure Analysis: Crystal data and refinement parameters
are collected in Table 5. All structures were solved by direct methods
1
9
–
1
28w, 859w, 842w, 832w, 821vs, 746s, 727s, 701vs, 663s cm .
[
38]
[39]
(
SIR92
for 1, 2, 3a, 3b and 4a, SIR2011
for 4b), completed by
subsequent difference Fourier syntheses, and refined by full-matrix le-
General Procedure for the Synthesis of the Dichloride Iron(II)
Complexes: FeCl ·(H O) was dissolved in 5 mL of dry MeOH and
ligand 3a resp. 3b was added whilst stirring. The color of the solution
[
40]
ast-squares procedures.
Semi-empirical absorption corrections from
2
2
4
equivalents (Multiscan) were carried out for 1, 2, 3a and 3b, while
analytical numeric absorption corrections were applied on complexes
turned immediately to orange-red. The reacting mixture was stirred for
[
41]
4a and 4b.
All non-hydrogen atoms were refined with anisotropic
3
2
h at room temp. Then the volume of the solvent was reduced to
mL and 25 mL of dry diethyl ether were added slowly to precipitate
displacement parameters. In the structure of compound 1 the hydrogen
atoms which are bound to the oxygen atoms O1 and O3, were located
in the difference Fourier synthesis, and were then refined freely. The
hydrogen atoms, which are bound to the nitrogen atoms N2 and N4 in
the structure of compound 2, were located in the difference Fourier
synthesis, and were refined semi-freely with the help of a distance
restraint, while constraining their U-values to 1.2 times the U(eq) val-
ues of corresponding nitrogen atoms. All the other hydrogen atoms
were placed in calculated positions and refined by using a riding
the product. The received red solids were recrystallized from dry
MeOH/diethyl ether.
[
2,6-Bis(N-methyl-(1R,4R)-1,7,7-trimethylbicyclo[2.2.1]heptanyl-
pyrazol-3-yl)pyridine]dichloridoiron(II) (4a): Synthesized from
7.7 mg (0.29 mmol) of FeCl ·(H O) and 151 mg (0.33 mmol) of 3a.
Yield 120 mg (71%). C29 FeN ·CH OH: calcd. C 58.64, H 6.73,
N 11.40%; found C 58.76, H 6.74, N 10.97%. IR (ATR): ν˜ = 2959w,
5
2
2
4
H37Cl
2
5
3
2
1
6
876w, 1604w, 1572w, 1550w, 1451s, 1413w, 1351m, 1303w, 1286m, model.
271w, 1248w, 1155m, 1122m, 1051w, 841w, 819s, 779w, 746m,
–1
Crystallographic data (excluding structure factors) for the structures in
this paper have been deposited with the Cambridge Crystallographic
Data Centre, CCDC, 12 Union Road, Cambridge CB21EZ, UK. Copies
91w, 662w cm .
[
2,6-bis(N-benzyl-(1R,4R)-1,7,7-trimethylbicyclo[2.2.1]heptanyl-
pyrazol-3-yl)pyridine]dichloridoiron(II) (4b): Synthesized from of the data can be obtained free of charge on quoting the depository
7.6 mg (0.349 mmol) of FeCl ·(H O) and 207 mg (0.34 mmol) of numbers CCDC-1968102, CCDC-1968103, CCDC-1968104, CCDC-
ligand 3b. Yield: 175 mg (70%). C41 FeN : calcd. C 67.04, H 1968105, CCDC-1968106, and CCDC-1968107 (Fax: +44-1223-336-
.17, N 9.53%; found C 66.74, H 6.21, N 9.48%. IR (ATR): ν˜ = 033; E-Mail: deposit@ccdc.cam.ac.uk, http://www.ccdc.cam.ac.uk).
6
2
2
4
H45Cl
2
5
6
Z. Anorg. Allg. Chem. 2020, 968–977
www.zaac.wiley-vch.de
975
© 2020 The Authors. Published by WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim