=
0.0520), R
1 2
= 0.0447, wR = 0.0822 [I > 2s(I)]. The ratio of the two
enantiomorphic components was refined to a value of 0.461(13).
For 2: C42H70Cl
2
FeMg0.5
3
N , M = 1545.71, monoclinic, space group
1
P2 /c, a = 12.6469(8), b = 13.0103(8), c = 26.414(2), b = 102.853(1), U
3
21
=
4237.3(5) Å , T = 193(2) K, Z = 2, m(Mo-Ka) = 0.526 mm , 18679
1 2
reflections measured, 6069 unique (Rint = 0.0551), R = 0.0546, wR =
0
.1361 [I > 2s(I)].
For 3: C35 53ClFeN
6.9014(11), b = 9.3514(6), c = 22.7756(15), b = 107.237(1), U =
H
2
, M = 593.09, monoclinic, space group C2/c, a =
1
3
3
21
428.0(4) Å , T = 193(2) K, Z = 4, m(Mo-Ka) = 0.540 mm , 7361
reflections measured, 2463 unique (Rint = 0.0256), R
.0704 [I > 2s(I)].
CCDC reference numbers 167176–167180. See http://www.rsc.org/
1
= 0.0398, wR =
2
0
suppdata/cc/b1/b103635c/ for crystallographic data in CIF or other
electronic format.
Fig. 4 Molecular structure of LAFeCl 3. Hydrogen atoms not shown, thermal
ellipsoids at 50% probability. Selected bond lengths (Å) and angles (°):
Fe(1)–N(11) 1.948(2), Fe(1)–Cl(1) 2.172(1); N(11)–Fe(1)–N(11)A
§ 1b: meff = 4.4 m
¶ LMgCl(THF): Yield 75%, d
Ar-H), 4.95 (s, 1H, CH), 3.63 (br s, 4H, CH
B
(Evans), meff = 5.4 m
B
(SQUID, 5000 G, 50–300 K).
, 23 °C) 7.2–7.3 (br s, 6H,
), 3.94 (br s, 4H, CH(CH ),
), 1.39 (br s, 24H, CH(CH ).
(400 MHz,
H
(400 MHz, C D
6 6
96.35(11), N(11)–Fe(1)–Cl(1) 131.83(5).
2
3 2
)
1
.78 (s, 6H, CH
3
), 1.48 (br s, 4H, CH
2
3 2
)
∑
2: Yield 60% based on FeCl
2
(THF)1.5, mp 302–304 °C, d
H
highly air-sensitive red solid 3 can be isolated.** The molecular
structure of the product LAFeCl 3 was determined by X-ray
crystallography (Fig. 4).‡ The iron and chlorine atoms are on a
crystallographic mirror plane. The iron atom lies in a planar ring
formed with the ligand; the bond angles around the metal reveal
a planar geometry (sum of angles = 360°). The N(11)–Fe(1)–
N(11)A bond angle is compressed to 96.35(11)°, while the
N(11)–Fe(1)–Cl(1) angle opens up to 131.83(5)°. As expected,
the lower coordination number of the iron atom in 3 causes the
bond lengths to the metal to decrease as compared to 1 and 2.
THF-d
8
, 23 °C) 13.58, 12.95, 5.68, 20.97, 21.25, 21.74, 22.63, 220.76,
28.13, 241.02, 247.98, 269.77; meff = 4.2 m
* 3: Yield 88% based on FeCl (THF)1.5, mp 270–272 °C (Anal. Found: C,
0.26; H, 8.86; N, 4.77. C35 53ClFeN requires C, 70.69; H, 8.42; N,
.61%); d (400 MHz, C , 23 °C) 48.78, 2.35, 1.21, 0.40, 225.84,
2
B
.
*
7
4
2
H
2
H
6 6
D
2105.33, 2115.05; m = 5.5 mB (Evans), m = 5.9 mB (SQUID, 5000 G,
50–300 K).
eff
eff
1 C. C. Cummins, Prog. Inorg. Chem., 1998, 47, 685; S. Alvarez, Coord.
Chem. Rev., 1999, 193–195, 13.
2
J. Kim and D. C. Rees, Nature, 1992, 360, 553; J. B. Howard and D. C.
Rees, Chem. Rev., 1996, 96, 2965; D. C. Rees and J. B. Howard, Curr.
Opin. Chem. Biol., 2000, 4, 559.
B B
Both the solution (meff = 5.5 m ) and solid state (meff = 5.9 m )
magnetic moments confirm the high-spin iron(II) oxidation
1
state. The H NMR spectrum is relatively simple, consisting of
3
4
Handbook of Heterogeneous Catalysis, ed. G. Ertl, H. Knözinger and J.
Weitkamp, Wiley-VCH, Weinheim, 1997, vol. 4.
seven paramagnetically shifted resonances.
While the effect of the ligand backbone groups on the
coordination number of iron may not be immediately obvious,
it can be understood by examining the C–N–C bond angles in
the three complexes. In 1 they are in the range 118.6–120.3°,
while in 3 they are 128.4(2)°. Thus, the tert-butyl groups on the
ligand backbone in LA force the aryl rings to close in on the
metal, limiting the space available at the iron centre for more
ligands.
P. H. M. Budzelaar, R. de Gelder and A. W. Gal, Organometallics,
1998, 17, 4121; M. Cheng, E. B. Lobkovsky and G W. Coates, J. Am.
Chem. Soc., 1998, 120, 11018; P. L. Holland and W. B. Tolman, J. Am.
Chem. Soc., 1999, 121, 7270; C. E. Radzewich, I. A. Guzei and R. F.
Jordan, J. Am. Chem. Soc., 1999, 121, 8673; M. Cheng, A. B. Attygalle,
E. B. Lobkovsky and G. W. Coates, J. Am. Chem. Soc., 1999, 121,
1
1583; C. Cui, H. W. Roesky, H.-G. Schmidt, M. Noltemeyer, H. Hao
and F. Cimpoesu, Angew. Chem., Int. Ed., 2000, 39, 4274; V. C. Gibson,
J. A. Segal, A. J. P. White and D. J. Williams, J. Am. Chem. Soc., 2000,
In most three-coordinate complexes of Fe(II),1,11 functional-
isation, if it is achieved, is usually at the expense of the low
coordination number. In contrast, complex 3 presents many
viable pathways for further functionalisation by reactions with
the chloride ligand while maintaining the low coordination
number.
1
22, 7120; N. J. Hardman, B. E. Eichler and P. P. Power, Chem.
Commun., 2000, 1991; P. J. Bailey, R. A. Coxall, C. M. Dick, S. Fabre
and S. Parsons, Organometallics, 2001, 20, 798; A. Akkari, J. J. Byrne,
I. Saur, G. Rima, H. Gornitzka and J. Barrau, J. Organomet. Chem.,
2001, 622, 190; N. J. Hardman, C. Cui, H. W. Roesky, W. H. Fink and
P. P. Power, Angew. Chem., Int. Ed., 2001, 40, 2172.
5
J. Feldman, S. J. McLain, A. Parthasarathy, W. J. Marshall, J. C.
Calabrese and S. D. Arthur, Organometallics, 1997, 16, 1514.
R. J. Kern, J. Inorg. Nucl. Chem., 1962, 24, 1105.
A. G. Orpen, L. Brammer, F. H. Allen, O. Kennard, D. G. Watson and
R. Taylor, J. Chem. Soc., Dalton Trans., 1989, S1.
The University of Rochester is gratefully acknowledged for
funding of this work. We would like to thank Kevin Mooney
6
7
(University at Buffalo) for recording the SQUID data.
8
C. D. Burbridge and D. M. L. Goodgame, J. Chem. Soc. A, 1968,
Notes and references
1
074.
†
1a: Yield 90% based on FeCl
Found: C, 63.88; H, 8.37; N, 4.11. C37
H, 8.25; N, 4.02%), d (400 MHz, C
2
(THF)1.5, mp 310 °C (decomp.) (Anal.
57Cl FeLiN requires C, 63.89;
, 23 °C) 17.08, 15.33, 9.19, 6.42,
9 M. V. Baker, L. D. Field and T. W. Hambley, Inorg. Chem., 1988, 27,
2872.
10 P. H. M. Budzelaar, A. B. van Oort and A. G. Orpen, Eur. J. Inorg.
Chem., 1998, 1485.
H
2
2 2
O
H
6
D
6
5
.15, 2.67, 1.99, 1.14, 0.93, 0.31, 212.89, 213.14, 216.93, 224.25,
2
35.43, 240.44, 244.60, 265.39; d
H
(THF-d
8
, 23 °C) 15.28, 6.98, 216.77,
11 W. Seidel and K.-J. Lattermann, Z. Anorg. Allg. Chem., 1982, 488, 69;
D. M. Roddick, T. D. Tilley, A. L. Rheingold and S. J. Geib, J. Am.
Chem. Soc., 1987, 109, 945; P. P. Power and S. C. Shoner, Angew.
Chem., Int. Ed. Engl., 1991, 30, 330; F. M. MacDonnell, K. Ruhlandt-
Senge, J. J. Ellison, R. H. Holm and P. P. Power, Inorg. Chem., 1995, 24,
1815; S. L. Stokes, W. M. Davis, A. L. Odom and C. C. Cummins,
Organometallics, 1996, 15, 4521; M. A. Putzer, B. Neumüller, K.
Dehnicke and J. Magull, Chem. Ber., 1996, 129, 715; U. Siemeling, U.
Vorfeld, B. Neumann and H.-G. Stammler, Inorg. Chem., 2000, 39,
5159.
2
43.60, 264.68.
‡
Crystal data For 1a: C37
H57Cl
2 2 2
FeLiN O , M = 695.54, orthorhombic,
space group Pna2
=
reflections measured, 10201 unique (Rint = 0.0307), R
0
1
, a = 23.1015(12), b = 9.9748(5), c = 35.9530(18), U
7786.4(7) Å , T = 193(2) K, Z = 8, m(Mo-Ka) = 0.556 mm , 32164
3
21
1
= 0.0478, wR
2
=
.0967 [I > 2s(I)].
For 1b: orthorhombic, space group P2 2 2 , a = 16.7761(8), b
1 1 1
=
3
19.0238(9), c = 36.8905(19), U = 11773.4(10) Å , T = 193(2) K, Z = 12,
21
m(Mo-Ka) = 0.556 mm , 53706 reflections measured, 16937 unique (Rint
Chem. Commun., 2001, 1542–1543
1543