214
C.D. Hall et al. / Journal of Organometallic Chemistry 561 (1998) 209–219
Table 2
The 13C-NMR spectra of 9 and complexes with CuBF4 and AgBF4
OCH3 CH2 Ch,i, cp
C
C
Cimino
158.7
160.6
163.6
l(ppm)a
55.5 62.0 66.3, 68.5, 69.4
85.2 111.0 (CH), 124.5 (C), 124.6 (CH), 129.4 (CH), 131.4 (C), 157.2 (C)
85.5 112.5 (CH), 125.1 (CH), 131.8 (C), 132.2 (CH), 158.4 (C)
(cp)
CuBF4 l (ppm)b 56.4
AgBF4 l (ppm)c 57.2
62.0 66.7, 69.6, 70.1
(cp)
62.9 68.0, 70.3, 71.0
(cp)
86.7 112.3 (CH), 124.2 (C), 124.5 (CH), 133.0 (CH),133.5 (C), 159.2 (C)
a Recorded in CDCl3.
b Recorded in CD3CN:CDCl3 (1:1).
c Recorded in CD3CN:CDCl3 (1:4).
N
4.67; found,
C
55.74,
H
4.92,
N
4.69. 1H
2.7. Synthesis of 1,1%-{bis(4-methoxy-3-propanyl-
imino)phenyl}ferrocenophane (12)
(CD3CN:CDCl3 1:4): 3.39 (br, 2H), 3.87 (s, 3H), 3.96
(s, 5H), 4.23 (s, 2H), 4.43 (s, 2H), 6.92 (d, 1H, J=8.7
Hz), 7.66 (dd, 1H, J=8.7 Hz), 7.80 (d, 1H, J=2.2 Hz),
8.61 (s, 1H). 13C (CD3CN:CDCl3 1:4): 57.2 (OCH3),
62.9 (CH2), 68.0 (fc), 71.0 (unsubst fc), 86.7 (ipso),
112.3 (CH), 124.2 (CH), 124.5 (CH), 133.0 (CH), 133.5
(C), 159.2 (C), 163.6 (CH).
Potassium carbonate (61 mg, 4.4×10−4 mol) and
manganous perchlorate hexahydrate (40 mg, 1.1×10−
4 mol) were added to a solution of (7, 50 mg, 1.2×10−
4
mol) in
a
1:1 (v/v) mixture of degassed
dichloromethane and methanol (40 ml). The mixture
was stirred for 3 h at r.t. when the orange solution
darkened. A solution of 1,3-diaminopropane (8.2 mg,
1.1×10−4 mol) in methanol (5 ml) was then added and
the resulting mixture was stirred at r.t. for 5 h. A dark
precipitate was filtered off and the filtrate evaporated.
The residue was recrystallized from methanol (0.5 ml)
to give an orange precipitate (19 mg, 34%). m.p.:dec\
165°C. RMM:FAB 493 (M+1); calculated for
C29H28N2O2Fe·4H2O: C 61.71, H 6.43, N 4.96; found
C 60.69, H 5.97, N 4.97. 1H (CDCl3): 2.33 (m, 2H), 3.79
(s, 6H), 3.91 (m, 4H), 4.27 (t, 4H, J=1.9 Hz), 4.57 (t,
4H, J=1.9 Hz), 6.50 (d, 2H, J=8.6 Hz), 7.01 (dd, 2H,
J=8.6 Hz), 7.72 (d, 2H, J=2.4 Hz), 8.58 (s, 2H). 13C
(CDCl3): 29.4 (CH2), 55.5 (OCH3), 63.6 (CH2) 66.2 (fc),
68.6 (fc), 86.2 (ipso), 110.8 (CH), 124.3 (CH), 128.0 (C),
128.4 (CH), 157.0 (CH). A water peak was also in
evidence.
2.8.2. Bis(3-ethylenediimino-4-methoxyphenyl)ferrocene
copper tetrafluoroborate
A
stirred solution of bis(3-ethylenediimino-4-
methoxyphenyl)ferrocene (9, 51 mg, 7.7×10−3 mmol)
in degassed acetonitrile (20 ml) was treated with
cuprous[tetrakis(acetonitrile)]-tetrafluoroborate,
Cu-
(CH3CN)4BF4, (24 mg, 0.077 mmol) in acetonitrile and
the mixture was stirred overnight. Diethylether (100 ml)
was then added to the orange solution and a dark
orange precipitate formed, which was collected and
dried under vacuum (55 mg, 83%). m.p. 170–176°C
(dec); RMM:FAB 857 (ligand+CuBF4+CH3CN); IR
1623 cm−1
.
Calculated for C38H36N2O2F4Cu-
BFe20.5CH3CN.2H2O: C 53.76, H 4.80, N 4.02; found
C 53.53, H 4.55, N 4.10. UV (CH2Cl2): u, 240, 284, 334,
450 nm (m=17760 1 mol−1 cm−1). 1H (CD3CN/
CDCl3): 3.62 (br, 2H), 3.91 (s, 6H), 4.02 (s, 10H), 4.31
(s, 4H), 4.61 (s, 4H), 7.03 (d, 2H, J=8.6 Hz), 7.74 (d,
2H, J=8.3 Hz), 8.17 (br, 2H), 8.73(br, 2H). 13C
(CD3CN/CDCl3): 56.4 (OCH3), 62.0 (CH2), 66.7 (fc),
69.6 (fc), 70.1 (unsubst. fc), 85.5 (ipso), 112.5 (CH),
125.1 (CH), 131.8 (C), 132.2 (CH), 158.4 (C), 160.6
(CH). Water and acetonitrile were also evident in the
1H-NMR spectrum.
2.8. Complexation of Schiff base ferrocene ligands
2.8.1. Bis(3-ethylenediimine-4-methoxyphenyl)ferrocene
sil6er tetrafluoroborate
A
stirred solution of bis(3-ethylenediimine-4-
methoxyphenyl)ferrocene (9, 30 mg, 0.045 mmol) in
degassed acetonitrile (20 ml) was treated with silver
tetrafluoroborate (9 mg, 0.045 mmol) and the mixture
was stirred overnight. Diethylether (100 ml) was then
added to the yellow, cloudy solution and the precipitate
formed was collected and dried as a yellow/brown
powder, which was redissolved in dichloromethane/ace-
tonitrile (4:1) and filtered twice. Evaporation gave or-
ange crystals of the complex (20 mg, 53%). m.p.
105–110°C, RMM:FAB 753 (ligand+Ag). Calculated
for C38H36N2O2F4BAgFe2+CH3CN: C 53.37, H 4.37,
2.9. Complexation of 1,1%-{bis(4-methoxy-3-propanyl-
imino)phenyl} ferrocenophane, 12, by NMR
2.9.1. 1,1%-{Bis(4-methoxy-3-propanyl-imino)phenyl}-
ferrocenophane copper tetrafluoroborate
A
mixture of 1,1%-{bis(4-methoxy-3-propanyl-
imino)phenyl}ferrocenophane (10 mg, 10−5 mol) in