Organometallics
Article
1
4
g (yield: 75%; color: orange). Anal. Calcd for C H Fe N O : C,
(CDCl ) δ 288.6 (μ-CO); 218.0 (CO); 186.7 (CO Me); 173.6 (C );
3 2
25
26
2
2
5
3
5
(
(
1
4
(
(
4.98; H, 4.80; N, 5.13. Found: C, 55.02; H, 4.76; N, 5.14. IR
147.8 (C ); 136.2 (ipso-Ph); 128.4, 127.1, 126.6 (Ph); 87.8, 84.3 (Cp);
67.6, 57.7 (NCH ); 61.1 (C ); 57.7 (CH Ph); 50.4 (CO Me); 40.9
1
2
CH Cl ): ν(CO) 1923 (vs), 1740 (s), 1660 (w), ν(C N) 1613
2
2
2
2
2
−
1
−1 1
m) cm . IR (KBr): ν(NH) 3108 (w-m) cm . H NMR (CDCl ) δ
(NMe).
Reactions of 1a−c with Hydrazine. Syntheses of [Fe {μ-
3
1.78 (br, 1 H, NH); 7.01−6.51 (4 H, C H ); 4.52, 4.37 (s, 10 H, Cp);
.20, 3.61 (d, 2 H, J = 20 Hz, C H ); 3.89 (s, 3 H, CO Me); 3.76
s, 3 H, OMe); 2.86 (s, 3 H, NMe). C{ H} NMR (CDCl ) δ 289.7
μ-CO); 218.6 (CO); 187.4 (CO Me); 170.3 (C ); 158.3 (ipso-
C H OMe); 148.0 (C ); 137.3, 127.8, 114.8 (C H OMe); 87.4, 84.2
Cp); 67.9 (C ); 55.4 (OMe); 50.5 (CO Me); 39.3 (NMe).
6
4
2
2 2
HH
1
1
1
3
2
1
η (C):η (N):η (C)-C (CO
Me)C H
C {N(Me)(R)}(NNH )}(μ-CO)(CO)-
2
2
2
2
2
1
3
1
(
Cp) ] [R = Me, 5a; R = 4-C H OMe, 5b; R = CH Ph, 5c]. A solution of
2
6
4
2
3
1
1
a (94 mg, 0.161 mmol), in THF (10 mL), was treated with a large
NH ·2H O (80% W/W, 1.0 mL, d = 1.03 g/mL). The
mixture was stirred for 15 min, and then filtered on alumina. Hence,
the volatiles were removed, and the residue was dissolved in CH Cl
and chromatographed on alumina. Elution with a 1:1 mixture of THF
and CH Cl gave an orange band corresponding to 5a. The product
was obtained as a microcrystalline powder upon removal of the
solvent. Yield: 58 mg, 77%. Anal. Calcd for C19 : C, 48.65;
H, 4.94; N, 8.96. Found: C, 48.50; H, 5.12; N, 9.02. IR (CH Cl ):
2
3
excess of NH
6
4
6
4
2
2
2
2
(
2
4
h (yield: 70%; color: pale green). Anal. Calcd for C H Fe N O :
2
2
27
31
2
3
5
C, 55.04; H, 5.30; N, 7.13. Found: C, 55.10; H, 5.41; N, 7.00. IR
1
(
CH Cl ): ν(CO) 1928 (vs), 1745 (s), 1659 (w), ν(C N) 1625 (w)
2
2
2
2
−
1 1
cm . H NMR (CDCl ) δ 7.29−5.94 (8 H, C H OMe and NCH );
3
6
4
2
4
.51, 4.39 (s, 10 H, Cp); 3.94 (s, 3 H, CO Me); 3.90, 3.70 (d, 2 H,
H23Fe N O
2 3 4
2
2
2
13
1
JHH = 20 Hz, C H ); 2.88 (s, 3 H, NMe); NH not observed. C{ H}
2
2
2
−
1
ν(CO) 1927 (vs), 1742 (s), 1665 (w), ν(CN) 1631 (w) cm . IR
NMR (CDCl ) δ 291.1 (μ-CO); 217.2 (CO); 186.5 (CO Me); 175.1
3
2
−1 1
1
3
(
KBr): ν(NH) 3242 (w-m) cm . H NMR (CDCl ) δ 4.51, 4.46 (s,
(
(
(
C ); 157.3 (ipso-C H OMe); 149.4 (C ); 139.1, 126.2, 113.7
3
6
4
2
2
1
C H
0 H, Cp); 4.05 (s, 2 H, NH ); 3.94, 3.46 (d, 2 H, J = 21 Hz,
2 HH
C H OMe); 87.9, 84.1 (Cp); 67.5, 58.7 (NCH ); 63.6 (C ); 50.7
6
4
2
2
13
1
CO Me); 41.9 (NMe).
4
2
); 3.93 (s, 3 H, CO
2
Me); 2.36 (s, 6 H, NMe). C{ H} NMR
2
1
i (yield: 68%; color: ochre yellow). Anal. Calcd for C H -
(CDCl
3
) δ 287.9 (μ-CO); 217.4 (CO); 186.6 (CO
2
Me); 161.6 (C );
Me); 37.8 (NMe).
Compounds 5b−c were prepared by the same procedure described for
5a, by reacting NH NH ·2H O with 1b and 1c, respectively. Crystals
32
32
3
2
Fe N O : C, 60.40; H, 5.07; N, 4.40. Found: C, 60.30; H, 5.16; N,
150.7 (C ); 87.7, 84.1 (Cp); 56.4 (C ); 50.7 (CO
2
2
2
5
1
4
1
5
.39. IR (CH Cl ): ν(CO) 1929 (vs), 1754 (s), 1669 (w), ν(C N)
2
2
−
1 1
645 (w) cm . H NMR (CDCl ) δ 8.16−6.32 (9 H, Ph and C H );
2
2
2
3
6
4
.65, 5.30 (br, 2 H, NCH ); 4.58, 4.35 (s, 10 H, Cp); 4.22, 3.60 (d, 2
of 5b suitable for X-ray analysis were collected by a CH
layered with n-pentane and stored at −20 °C.
2
Cl
2
solution
2
2
2
H, J = 18.7 Hz, C H ); 3.94 (s, 3 H, CO Me); 3.76 (s, 3 H, OMe);
HH
2
2
1
3
1
2
.80 (s, 3 H, NMe). C{ H} NMR (CDCl ) δ 287.3 (μ-CO); 218.0
5b (yield: 78%; color: orange). Anal. Calcd for C25
H
27Fe
2
N
3
O
5
: C,
3
1
(
(
(
CO); 186.9 (CO Me); 170.0 (C ); 155.3 (ipso-C H OMe); 148.8
53.51; H, 4.85; N, 7.49. Found: C, 53.57; H, 4.96; N, 7.55. IR
2
6
4
3
C ); 139.0, 123.9, 114.0 (C H OMe and Ph); 87.8, 83.8 (Cp); 63.0
(CH Cl
2
2
): ν(CO) 1930 (vs), 1748 (s), 1666 (w), ν(CN) 1630 (w)
6
4
2
−1
−1 1
NCH ); 61.2 (C ); 55.0 (OMe); 50.9 (CO Me); 41.1 (NMe).
4
cm . IR (KBr): ν(NH) 3364, 3270 (w-m) cm . H NMR (CDCl
6.76, 6.49 (d, 4 H, JHH = 8.79 Hz, C
3
) δ
2
2
3
j (yield: 75%; color: ochre yellow). Anal. Calcd for C H -
6
H
2
4
); 4.56, 4.51 (s, 10 H, Cp);
26
28
2
2
Fe N O : C, 57.38; H, 5.19; N, 5.15. Found: C, 57.42; H, 5.12; N,
4.09, 3.67 (d, 2 H, JHH = 20.9 Hz, C H
3 H, CO
NMR (CDCl
(ipso-C OMe); 155.6 (C ); 150.1 (C ); 138.4, 121.4, 114.3
(C OMe); 87.8, 84.1 (Cp); 56.6 (C ); 55.4 (OMe); 50.7
); 4.07 (s, 2 H, NH
2
); 3.94 (s,
2
2
5
1
13
1
5
1
(
(
.20. IR (CH Cl ): ν(CO) 1925 (vs), 1747 (s), 1664 (w), ν(C N)
2
Me); 3.75 (s, 3 H, OMe); 2.84 (s, 3 H, NMe). C{ H}
) δ 287.5 (μ-CO); 217.5 (CO); 186.1 (CO Me); 156.8
2
2
−
1 1
614 (m) cm . H NMR (CDCl ) δ 7.29−7.00 (5 H, Ph); 4.54, 4.40
3
2
3
2
2
1
3
s, 10 H, Cp); 4.12, 3.71 (d, 2 H, J = 20.49 Hz, C H ); 3.90, 3.80
H
6 4
HH
2
2
2
d, 2 H, J = 15.37 Hz, CH Ph); 3.94 (s, 3 H, CO Me); 2.47 (s, 3
H, NMe), 2.38 (s, 3 H, NMe). C{ H} NMR (CDCl ) δ 286.3 (μ-
CO); 217.9 (CO); 186.5 (CO Me); 173.5 (C ); 147.9 (C ); 137.0
ipso-Ph); 128.6, 127.3, 127.0 (Ph); 87.7, 84.4 (Cp); 60.6 (C ); 57.0
CH Ph); 50.6 (CO Me); 42.3 (NMe); 39.4 (NMe).
H
6 4
HH
2
2
1
3
1
(CO Me); 40.3 (NMe).
3
2
1
3
5c (yield: 72%; color: orange). Anal. Calcd for C H Fe N O : C,
55.08; H, 4.99; N, 7.71. Found: C, 54.96; H, 5.04; N, 7.80. IR
2
25 27
2
3
4
2
(
(
(CH Cl ): ν(CO) 1930 (vs), 1743 (s), 1666 (w), ν(CN) 1630 (w)
2
2
2
2
−
1
−1 1
4
k (yield: 81%; color: ochre yellow). Anal. Calcd for C H -
cm . IR (KBr): ν(NH) 3361, 3248 (w-m) cm . H NMR (CDCl ) δ
27
30
3
Fe N O : C, 58.09; H, 5.42; N, 5.02. Found: C, 58.04; H, 5.47; N,
7.30−7.01 (5 H, Ph); 4.54, 4.48 (s, 10 H, Cp); 4.14 (s, 2 H, NH );
2
2
4
2
1
2
2
4
.96. IR (CH Cl ): ν(CO) 1924 (vs), 1747 (s), 1664 (w), ν(C N)
4.01, 3.71 (d, 2 H, J = 14.6 Hz, CH Ph); 3.9, 3.6 (d, 2 H, J
=
2
2
HH
2
HH
−1
1
2
13
1
1
625 (w) cm . H NMR (CDCl ) δ 7.32−7.00 (5 H, Ph); 4.51, 4.37
21.96 Hz, C H ); 3.93 (s, 3 H, CO Me); 2.33 (s, 3 H, NMe). C{ H}
3
2
2
2
2
(
s, 10 H, Cp); 4.23, 3.64 (d, 2 H, J = 21 Hz, C H ); 3.91 (s, 3 H,
NMR (CDCl ) δ 287.5 (μ-CO); 217.3 (CO); 186.1 (CO Me); 161.6
3 2
HH
2
2
1
3
CO Me); 3.90, 3.80 (d, 2 H, J = 15 Hz, CH Ph); 2.93, 2.66 (m, 2
H, NCH CH ); 2.37 (s, 3 H, NMe); 1.00 (t, 3 H, J = 7 Hz,
NCH CH ). C{ H} NMR (CDCl ) δ 286.9 (μ-CO); 218.0 (CO);
(C ); 150.1 (C ); 137.1, 128.5, 127.7, 127.4 (Ph); 87.7, 84.1 (Cp);
2
HH
2
3
2
2
3
HH
56.3 (C ); 54.9 (CH Ph); 50.7 (CO Me); 37.8 (NMe).
2
2
1
3
1
1
3
3
2
3
3
Conversion of 5 to 6. Syntheses of [Fe {μ-η :η -C (CO Me)-
C HC HN(Me)(4-C
= CH Ph, 6b]. Complex 5b (90 mg, 0.160 mmol), was dissolved in
2
2
2
1
3
2
1
186.6 (CO Me); 172.3 (C ); 148.0 (C ); 137.2 (ipso-Ph); 128.5,
6
H OMe)}(CO)(μ-CO)(Cp)
4
2
] [R = C H
6
4
OMe, 6a; R
2
2
1
27.3, 127.0 (Ph); 87.9, 84.3 (Cp); 61.8 (C ); 57.8 (CH Ph); 50.6
2
(
CO Me); 49.6 (NCH CH ); 39.7 (NMe); 14.2 (NCH CH ).
toluene (15 mL), and the solution was stirred at boiling temperature
for 4 h. Hence, the solution was allowed to cool to room temperature
and, then, chromatographed on an alumina column. Elution with
2
2
3
2
3
4
l (yield: 81%; color: ochre yellow). Anal. Calcd for C H -
29 34
Fe N O : C, 59.41; H, 5.85; N, 4.78. Found: C, 59.41; H, 5.75; N,
4
1
2
2
4
1
.89. IR (CH Cl ): ν(CO) 1925 (vs), 1752 (s), 1664 (w), ν(C N)
CH
solid upon removal of the solvent. Yield: 48 mg, 56%. Anal. Calcd for
NO : C, 56.53; H, 4.74; N, 2.64. Found: C, 56.60; H, 4.69;
N, 2.58. IR (CH
NMR (CDCl ) δ 7.29, 6.94, 6.78, 6.57 (d, 4 H, JHH = 8.42 Hz, C
4.70, 4.46 (s, 10 H, Cp); 4.81 (d, 2 H, JHH = 9.6 Hz, C H); 4.09 (s, 3
H, CO Me); 3.80 (s, 3 H, OMe); 2.77 (s, 3 H, NMe); 1.82 (d, 2 H,
2 2
Cl gave a green band, corresponding to 6a which was obtained as
2
2
−
1 1
643 (w) cm . H NMR (CDCl ) δ 7.32−6.94 (5 H, Ph); 4.46, 4.31
3
2
2
(
s, 10 H, Cp); 4.23, 3.78 (d, 2 H, J = 20.5 Hz, C H ); 3.86 (s, 3 H,
C
25
H25Fe
2
5
HH
2
2
−1 1
CO Me); 3.73, 3.65 (d, 2 H, J = 15.4 Hz, CH Ph); 2.76, 2.48, 1.92,
Cl ): ν(CO) 1942 (vs), 1765 (s), 1693 (m) cm . H
2 2
2
HH
2
3
1
(
.47, 1.32, 1.20 (m, 6 H, NCH CH CH ); 2.31 (s, 3 H, NMe); 0.85
3
H );
6 4
2
2
2
13
1
3
2
m, 3 H, NCH CH CH CH ). C{ H} NMR (CDCl ) δ 286.9 (μ-
2 2 2 3 3
1
3
CO); 218.0 (CO); 186.6 (CO Me); 172.4 (C ); 147.9 (C ); 137.1
2
2
2
3
1
(
(
(
ipso-Ph); 135.6, 128.5, 126.9 (Ph); 87.9, 84.3 (Cp); 61.8 (C ); 57.8
CH Ph); 55.6, 30.8, 20.6 (NCH CH CH ); 50.6 (CO Me); 39.6
J
HH = 9.6 Hz, C H).
2
2
2
2
2
Complex 6b was obtained by an analogous procedure described for
6a starting from 5c (yield: 58%). Complex 6b was identified upon
NMe); 13.8 (NCH CH CH CH ).
2
2
2
3
4
m (yield: 77%; color: pale green). Anal. Calcd for C H Fe N O :
comparison of its spectroscopic properties with those reported in the
27
31
2
3
4
4
C, 56.57; H, 5.45; N, 7.33. Found: C, 56.68; H, 5.30; N, 7.20. IR
literature.
1
1
1
1
3
2
1
(
CH Cl ): ν(CO) 1925 (vs), 1744 (s), 1665 (w), ν(C N) 1596 (w)
Synthesis of [Fe {μ-η (C):η (N):η (C)-C (CO Me)C (H)(D)C (NMe )-
2
2
2
2
2
−
1
−1
1
cm . IR (KBr): ν(NH) 3255 (w-m) cm . H NMR (CDCl ) δ
(NEt)}(μ-CO)(CO)(Cp) ] (7). A large excess of NH Et was bubbled into
2 2
3
7
4
.51−7.04 (5 H, Ph); 6.96, 6.76, 6.40, 6.03 (br, 4 H, NCH ); 4.53,
5.0 mL of D O, for 20 s. The solution was stirred for 2 h, and then it
was added to a THF solution (20 mL) of 1a (80 mg, 0.137 mmol).
The resulting mixture was stirred for 30 min and then filtered on an
2
2
2
2
.39 (s, 10 H, Cp); 3.95, 3.75 (d, 2 H, J = 20 Hz, C H ); 3.93 (s, 3
HH
2
13
1
H, CO Me); 2.26 (s, 3 H, NMe); NH not observed. C{ H} NMR
2
G
Organometallics XXXX, XXX, XXX−XXX