Reactivity of naphthylimines toward Fe2(CO)9: observation of three different hydrogen migration pathways

Article abstract of DOI:10.1021/om990067z

The reaction of Fe₂(CO)₉ with imine ligands derived from α- or β-naphthylcarbaldehydes leads to the formation of a series of iron carbonyl complexes. Most of them are produced by a C-H activation reaction in ortho position with respect to the exocyclic imine function. The reaction then proceeds via subsequent intramolecular hydrogen shift reactions and leads to several dinuclear compounds. Three different types of these hydrogen-transfer reactions were observed: a 1,3 hydrogen shift toward the former imine carbon atom, a 1,4 hydrogen shift toward the former imine nitrogen atom, or a 1,3 shift reaction toward one of the aromatic carbon atoms of the naphthalene system, which thus leaves the exocyclic imine function unreacted. In the reaction of β-naphthyl derivatives the formation of trinuclear complexes is observed by the η⁴-coordination of a third Fe(CO)₃ group to the second ring of the naphthalene. Besides this, the first example of a structurally characterized (η⁴-1-azadiene)-Fe(CO)₃ complex with the C-C double bond formally being part of a cyclic aromatic system is obtained as a byproduct.

Full text of DOI:10.1021/om990067z

Organometallics 1999, 18, 4845-4855
4845
Rea ctivity of Na p h th ylim in es tow a r d F e2(CO)9:
Obser va tion of Th r ee Differ en t Hyd r ogen Migr a tion
P a th w a ys#
Wolfgang Imhof*
Institut fu¨r Anorganische und Analytische Chemie, August-Bebel-Strasse 2,
07743 J ena, Germany
Received February 2, 1999
The reaction of Fe2(CO)9 with imine ligands derived from R- or â-naphthylcarbaldehydes
leads to the formation of a series of iron carbonyl complexes. Most of them are produced by
a C-H activation reaction in ortho position with respect to the exocyclic imine function.
The reaction then proceeds via subsequent intramolecular hydrogen shift reactions and leads
to several dinuclear compounds. Three different types of these hydrogen-transfer reactions
were observed: a 1,3 hydrogen shift toward the former imine carbon atom, a 1,4 hydrogen
shift toward the former imine nitrogen atom, or a 1,3 shift reaction toward one of the aromatic
carbon atoms of the naphthalene system, which thus leaves the exocyclic imine function
unreacted. In the reaction of â-naphthyl derivatives the formation of trinuclear complexes
is observed by the η4-coordination of a third Fe(CO)3 group to the second ring of the
naphthalene. Besides this, the first example of a structurally characterized (η4-1-azadiene)-
Fe(CO)3 complex with the C-C double bond formally being part of a cyclic aromatic system
is obtained as a byproduct.
In tr od u ction
pounds are formed by metalation of the ligand at the
imine carbon atom or in â-position and in some cases
by subsequent hydrogen shift reactions. The reaction
of Ru3(CO)12 with imines of benzaldehyde leads to the
formation of either mononuclear complexes of the
general formula Ru(imine)2(CO)2 with orthometalated
ligands or a trinuclear ruthenium cluster compound in
which the imine is only coordinated via its C-N double
bond.4 On the other side, it is well-known that 1-aza-
diene ligands react with Fe2(CO)9 to give mononuclear
complexes of the type (η4-azadiene)Fe(CO)3.5 In contrast
R,â-unsaturated imines in which the C-C double bond
is part of a heterocyclic or carbocyclic aromatic system
react with Fe2(CO)9 by means of a C-H activation
reaction in â-position to the exocyclic imine group.6 The
reaction then proceeds via a 1,3 hydrogen shift reaction
to produce a µ2-η3-enyl-amido ligand bridging an Fe2-
The understanding of C-H activation processes is one
important factor in the development of catalytic C-C
bond formation reactions. Due to this fact, both inter-
and intramolecular C-H activation reactions have been
intensively studied and thoroughly reviewed in the last
years.1 In recent times C-H activation reactions of
aromatic imines or ketones have been used to develop
catalytic C-C coupling reactions with CO and/or a wide
variety of olefins.2 So we are interested in the reactivity
of R,â-unsaturated imines toward metal carbonyls of
group 8 metals. The reactivity of imine ligands derived
from cinnamaldehyde toward Ru3(CO)12 has been re-
ported to yield a series of di-, tri-, and tetranuclear
ruthenium cluster compounds.3 These cluster com-
* Corresponding author. E-mail: cwi@rz.uni-jena.de.
#
Part of this work has been presented at the XIIth FECHEM
Conference on Organometallic Chemistry 1997, Prague, Czech Repub-
lic.
(4) (a) Bennett, R. L.; Bruce, M. I.; Goodall, B. L.; Iqbal, M. Z.; Stone,
F. G. A. J . Chem. Soc., Dalton Trans. 1972, 1787-1791. (b) Basu, A.;
Bhaduri, S.; Sharma, K.; J ones, P. G. J . Chem. Soc., Chem. Commun.
1987, 1126-1127.
(1) (a) Brookhart, M.; Green, M. L. H. J . Organomet. Chem. 1983,
250, 395-408. (b) Constable, E. C. Polyhedron 1984, 3, 1037-1057.
(c) Halpern, J . Inorg. Chim. Acta 1985, 100, 41-48. (d) Crabtree, R.
H. Chem. Rev. 1985, 85, 245-269. (e) Ryabov, A. D. Chem. Rev. 1990,
90, 403-424. (f) Davies, J . A., Ed. Selective Hydrocarbon Activation;
VCH: Weinheim, 1990. (g) Arndtsen, B. A.; Bergman, R. G.; Mobley,
T. A.; Petersen, T. H. Acc. Chem. Res. 1995, 28, 154-162. (h) Crabtree,
R. H. Chem. Rev. 1995, 95, 987. (i) Fujiwara, Y.; Takagi, K.; Taniguchi,
Y. Synlett 1996, 591-599.
(2) (a) Ketones: Sonoda, M.; Kakiuchi, F.; Chatani, N.; Murai, S.
Bull. Chem. Soc. J pn. 1997, 70, 3117-3128, and literature cited
therein. (b) Imines: Kakiuchi, F.; Yamauchi, F.; Chatani, N.; Murai,
S. Chem. Lett. 1996, 111-112. (c) Fukuyama, T.; Chatani, N.; Kakiuchi,
F.; Murai, S. J . Org. Chem. 1997, 62, 5647-5650. (d) Fukuyama, T.;
Chatani, N.; Tatsumi, J .; Kakiuchi, F.; Murai, S. J . Am. Chem. Soc.
1998, 120, 11522-11523.
(5) (a) Otsuka, S.; Yoshida, T.; Nakamura, A. Inorg. Chem. 1967, 6,
20-25. (b) De Cian, A.; Weiss, R. Acta Crystallogr. 1972, B28, 3264-
3280. (c) Brodie, A. M.; J ohnson, B. F. G.; J osty, P. L.; Lewis, J . J .
Chem. Soc., Dalton Trans. 1972, 2031-2035. (d) Semmelhack, M. F.;
Cheng, C. H. J . Organomet. Chem. 1990, 393, 237-241. (e) Kno¨lker,
H.-J .; Gonser, P. Synlett 1992, 517-520. (f) Kno¨lker, H.-J .; Gonser,
P.; J ones, P. G. Synlett 1994, 405-408. (g) Kno¨lker, H.-J .; Baum, G.;
Gonser, P. Tetrahedron Lett. 1995, 36, 8191-8194. (h) Kno¨lker, H.-J .;
Goesmann, H.; Gonser, P. Tetrahedron Lett. 1996, 37, 6543-6546. (i)
Kane-Maguire, L. A. P.; Pyne, S. G.; Siu, A. F. H.; Skelton, B. W. J .
Aust. Chem. 1996, 49, 673-676. (j) Kno¨lker, H.-J .; Baum, G.; Foitzik,
N.; Goesmann, H.; Gonser, P.; J ones, P. G.; Ro¨ttele, H. Eur. J . Inorg.
Chem. 1998, 993-1007. (k) Imhof, W.; Go¨bel, A.; Braga, D.; De
Leonardis, P.; Tedesco, E. Organometallics 1999, 18, 736.
(3) (a) Elsevier, C. J .; Mul, W. P.; Vrieze, K. Inorg. Chim. Acta 1992,
198-200, 689-703, and literature cited therein. (b) Imhof, W. J . Chem.
Soc., Dalton Trans. 1996, 1429-1436. (c) Mul, W. P.; Elsevier, C. J .;
Polm, L. H.; Vrieze, K.; Zoutberg, M. C.; Heijdenrijk, D.; Stam, C. H.
Organometallics 1991, 10, 2247-2259.
(6) (a) Imhof, W. J . Organomet. Chem. 1997, 533, 31-43. (b) Imhof,
W. J . Organomet. Chem. 1997, 541, 109-116. (c) Bagga, M. M.;
Flannigan, W. T.; Knox, G. R.; Pauson, P. L.; Preston, F. J .; Reed, R.
I. J . Chem. Soc. C 1968, 36-40. (d) Imhof, W.; Go¨bel, A.; Ohlmann,
D.; Flemming, J .; Fritzsche, H. J . Organomet. Chem. 1999, 584, 33.
10.1021/om990067z CCC: $18.00 © 1999 American Chemical Society
Publication on Web 10/20/1999

4846 Organometallics, Vol. 18, No. 23, 1999
Imhof
Sch em e 1
(CO)6 moiety. A compound of this type has first been
reported in ref 6c, where the reaction of benzylidene-
aniline with Fe2(CO)9 has been described. The structure
was correctly assigned on the basis of NMR data. The
same cluster compound is also available from the
reaction of Fe3(CO)12 with benzalazine.7 Only very
recently was the first complex of this type derived from
a cinnamaldehyde derivative obtained as a byproduct
in the synthesis of the corresponding η4-azadiene com-
pound.8 A complex that consists of a µ2-η3-enyl-amido
moiety bridging a dinuclear transition metal fragment
also was observed in the reaction of [CpCo(C2H4)2] with
N-phenylbenzylideneamine.9 Related iron compounds of
the formula [(R)N-C(H)-C(H)-Fe(CO)3-C(O)]Fe(CO)3
which show a keto group instead of the methylene group
in the above-mentioned compounds have been prepared
from the reaction of the carbene cluster (µ2-CH2)Fe2-
(CO)8 with phosphine imides in the presence of CO.10
Thermally induced rearrangement of those binuclear
cluster compounds yields the isomeric clusters [C(H)-
C(H)-N(R)-Fe(CO)3-C(O)]Fe(CO)3.10
In this report we describe the synthesis and charac-
terization of a series of iron cluster compounds derived
from the reaction of Fe2(CO)9 with imines of R- and
â-naphthylcarbaldehydes. The reaction proceeds via
C-H activation reactions in ortho position with respect
to the exocyclic imine group and subsequent intra-
molecular hydrogen shift reactions. In this context three
different types of hydrogen shift reactions will be
described. Up to now the reaction of Fe2(CO)9 with
imines from benzaldehyde or heterocyclic aromatic
imine ligands was described to include the 1,3 hydrogen
transfer reaction from the aromatic ring toward the
imine carbon atom.6 We also observed two new hydrogen
migration pathways, namely, the 1,4 hydrogen shift
toward the imine nitrogen atom as well as a 1,3
hydrogen transfer to one of the carbon atoms of the
naphthalene system. In addition the reaction of
Fe2(CO)9 with R-naphthylidene-N-cyclohexylimine leads
to the formation of a tetranuclear cluster compound of
the general formula (ligand)2Fe4(CO)10, which shows the
same structural features that have been observed for
related ruthenium compounds.3 The reaction of â-naph-
thylidene-N-phenylimine with Fe2(CO)9 on the other
hand as a byproduct yields the first example of a
mononuclear Fe(CO)3 complex of an azadiene in which
the C-C double bond is part of an aromatic system
which could also be structurally characterized.
Syn th eses of th e Com p ou n d s
The imine ligands are easily prepared by condensa-
tion of the naphthylcarbaldehydes with the correspond-
ing amines adding a catalytic amount of p-toluenesulfon-
ic acid. Both imines derived from R-naphthylcarbaldehyde
are yellow oils and may be purified by distillation,
whereas the ligands from â-naphthylcarbaldehyde are
solids that may be purified by recrystallization from
ethanol.
The reaction of Fe2(CO)9 with the imines from R-naph-
thylcarbaldehyde leads to the formation of the iron
cluster compounds 1-4 (Scheme 1). 1 and 2 are the
main products of the reactions, whereas 3 is only formed
for R being phenyl and the tetranuclear cluster com-
pound 4 is only produced with cyclohexyl being attached
to nitrogen. In all cases a C-H activation in ortho
position with respect to the exocyclic imine function is
observed. So in a first reaction step an iron hydride
species that is stabilized by the nitrogen lone pair of
the imine moiety in ortho position may be produced as
an intermediate. The formation of 1 and 2 further
proceeds by an intramolecular 1,3 hydrogen shift reac-
tion of the hydrogen atom toward the former imine
carbon atom, producing a methylene group instead. The
formation of 3 may be rationalized by an intramolecular
1,4 hydrogen shift reaction toward the former imine
nitrogen atom. In the formation of 4 no hydrogen shift
reaction is observed.
(7) (a) Nametkin, N. S.; Tyurin, V. D.; Trusov, V. V.; Batsanov, A.
S.; Struchkov, Y. T. J . Organomet. Chem. 1981, 219, C26-C28. (b)
Nametkin, N. S.; Tyurin, V. D.; Trusov, V. V.; Nekhaev, A. I.;
Alexandrov, G. G.; Parpiev, N. A.; Tashev, M. T.; Doustov, H. B. J .
Organomet. Chem. 1984, 276, 199-204. (c) Nametkin, N. S.; Tyurin,
V. D.; Trusov, V. V.; Nekhaev, A. I.; Batsanov, A. S.; Struchkov, Y. T.
J . Organomet. Chem. 1986, 302, 243-248.
(8) Kno¨lker, H.-J .; Baum, E.; Gonser, P.; Rohde, G.; Ro¨ttele, H.
Organometallics 1998, 17, 3916.
(9) Carofiglio, T.; Stella, S.; Floriani, C.; Chiesi-Villa, A.; Guastini,
C. J . Chem. Soc., Dalton Trans. 1989, 1957.
(10) (a) Mirkin, C. A.; Lu, K.-L.; Geoffroy, G. L.; Rheingold, A. L.;
Staley, D. L. J . Am. Chem. Soc. 1989, 111, 7279-7281. (b) Mirkin, C.
A.; Lu, K.-L.; Geoffroy, G. L.; Rheingold, A. L. J . Am. Chem. Soc. 1990,
112, 461-462. (c) Song, J .-S.; Han, S.-H.; Nguyen, S. T.; Geoffroy, G.
L.; Rheingold, A. L. Organometallics 1990, 9, 2386-2395. (d) Mirkin,
C. A.; Lu, K.-L.; Snead, T. E.; Young, B. A.; Geoffroy, G. L.; Rheingold,
A. L.; Haggerty, B. S. J . Am. Chem. Soc. 1991, 113, 3800-3810. (e)
Snead, T. E.; Mirkin, C. A.; Lu, K.-L.; Nguyen, S.-B. T.; Feng, W.-C.;
Beckmann, H. L.; Geoffroy, G. L. Organometallics 1992, 11, 2613-
2622.
The main products of the reaction of â-naphthylcar-
baldimines with Fe2(CO)9 (Scheme 2) are the dinuclear
cluster compounds 5 and 6, which show very similar

Reactivity of Naphthylimines toward Fe2(CO)9
Organometallics, Vol. 18, No. 23, 1999 4847
Ta ble 1. Bon d Len gth s [p m ] a n d An gles [d eg] of 1 a n d 2
1
Fe1-Fe2
Fe1-N1
C1-C10
244.7(2)
196.8(6)
140(1)
Fe1-C1
Fe2-C1
C10-C11
218.0(8)
198.8(8)
151(1)
Fe1-C10
Fe2-N1
C11-N1
230.2(8)
197.5(6)
146(1)
C1-Fe1-Fe2
C10-Fe1-Fe2
Fe1-Fe2-C1
Fe1-C1-C10
Fe1-N1-Fe2
C1-C10-C11
50.5(2)
73.8(2)
57.8(2)
76.5(5)
76.7(2)
114.3(7)
C1-Fe1-C10
C10-Fe1-N1
Fe1-Fe2-N1
Fe1-C10-C1
Fe1-N1-C11
C10-C11-N1
36.4(3)
64.5(3)
51.5(2)
67.1(5)
99.0(5)
101.3(6)
C1-Fe1-N1
N1-Fe1-Fe2
Fe1-C1-Fe2
Fe1-C10-C11
Fe2-C1-C10
C11-N1-Fe2
74.6(3)
51.8(2)
71.7(3)
84.5(5)
113.3(6)
111.8(5)
2
Fe1-Fe2
Fe1-N1
C1-C10
245.3(1)
197.2(3)
140.9(5)
Fe1-C1
Fe2-C1
C10-C11
214.1(4)
198.2(4)
149.8(6)
Fe1-C10
Fe2-N1
C11-N1
230.3(4)
197.5(3)
148.3(5)
C1-Fe1-Fe2
C10-Fe1-Fe2
Fe1-Fe2-C1
Fe1-C1-C10
Fe1-N1-Fe2
C1-C10-C11
50.6(1)
74.0(1)
56.5(1)
77.9(2)
76.8(1)
114.2(4)
C1-Fe1-C10
C10-Fe1-N1
Fe1-Fe2-N1
Fe1-C10-C1
Fe1-N1-C11
C10-C11-N1
36.8(1)
65.0(1)
51.51(9)
65.4(2)
97.7(2)
101.7(3)
C1-Fe1-N1
N1-Fe1-Fe2
Fe1-C1-Fe2
Fe1-C10-C11
Fe2-C1-C10
C11-N1-Fe2
75.0(1)
51.65(9)
72.9(1)
84.3(2)
114.3(3)
111.9(2)
Sch em e 2
F igu r e 1. Molecular structure of 2.
formation of 10 proceeds without a C-H activation
reaction but via the η4-coordination of an Fe(CO)3
moiety to the ligand through the C-N double bond of
the imine and the aromatic C-C bond between C2 and
C3 of the naphthalene system. This is the first time a
η4-coordination of a R,â-unsaturated imine ligand in
which the C-C bond is part of an aromatic system has
been structurally characterized.
In all reactions the compounds are separated and
purified by chromatography under inert conditions and
subsequent recrystallization from mixtures of light
petroleum/CH2Cl2 at -20 °C.
structural features compared to 1 and 2 and which are
formed in the same way. 7 is only produced in the
reaction with the ligand bearing a cyclohexyl group at
the nitrogen atom. In this reaction also an intramolecu-
lar 1,3 hydrogen shift reaction takes place, but the
hydrogen atom is transferred to the naphthalene sys-
tem, whereas the imine double bond remains unreacted.
The trinuclear iron cluster compounds 8 and 9 are
closely related to the compounds 5 and 6 since the C-H
activation hydrogen shift reaction sequence at the
naphthalene ring bearing the imine substituent pro-
ceeds the same way as in the formation of 5 and 6. In 8
and 9 the second ring of the naphthalene system is η4-
coordinated by an Fe(CO)3 moiety like in the well-known
(η4-butadiene)Fe(CO)3 complexes. In the formation of
5-9 the C-H activation reaction always takes place in
the 3-position of the naphthalene system. A reaction at
the other ortho position has never been observed. The
Cr ysta l Str u ctu r e Deter m in a tion s
Figure 1 shows the molecular structure of 2; the same
numbering scheme has been adopted in the structure
analysis of 1. The most important bond lengths and
angles have been summarized in Table 1. In both
compounds the naphthalene system has been metalated
in ortho position with respect to the exocyclic imine
group (C1). The hydrogen atom has been transferred
toward the former imine carbon atom (C11). Recently
we were able to show this process to proceed via a
strictly intramolecular pathway by using selectively
deuterated ligands.6d The complex thus may also be
described as an azaferracyclopentadiene derivative be-
ing coordinated to another apical Fe(CO)3 moiety. The
bond lengths at C11 are clearly single bonds, as is the
metal-metal bond. The only unusual feature is the very

4848 Organometallics, Vol. 18, No. 23, 1999
Ta ble 2. Bon d Len gth s [p m ] a n d An gles [d eg] of 3
Imhof
Fe1-Fe2
Fe1-C11
C1-C10
258.0(1)
204.3(5)
142.0(6)
Fe1-C1
Fe2-C1
C10-C11
211.1(4)
198.4(4)
144.2(6)
Fe1-C10
Fe2-N1
C11-N1
209.3(4)
206.2(4)
146.5(6)
C1-Fe1-Fe2
C1-Fe1-C10
Fe1-Fe2-C1
Fe1-C10-C1
Fe1-C11-N1
C10-C11-N1
48.8(1)
39.5(2)
53.2(1)
70.9(2)
104.7(3)
114.2(4)
C10-Fe1-Fe2
C1-Fe1-C11
Fe1-Fe2-N1
Fe1-C10-C11
Fe2-C1-C10
C11-N1-Fe2
74.3(1)
68.9(2)
73.3(1)
67.8(2)
112.5(3)
100.7(3)
C11-Fe1-Fe2
C10-Fe1-C11
Fe1-C1-C10
Fe1-C11-C10
C1-C10-C11
N1-Fe2-C1
71.7(1)
40.8(2)
69.6(2)
71.5(2)
110.5(4)
83.7(2)
F igu r e 2. Molecular structure of 3.
unsymmetrical coordination of Fe1 by C1 and C10,
formally the π-coordination of an aromatic double bond.
The iron carbon bond length between Fe1 and C1 is
about 12 pm (1) and 16 pm (2), respectively, shorter
than the bond between Fe1 and C10. It is very unlikely
that this effect is due to steric reasons since it is even
stronger for 5 and 6, as we will see below.
Figure 2 shows the result of the structure analysis of
3; the most important bond lengths and angles are
depicted in Table 2. In 3 the naphthalene system has
been metalated at C1, as it has been in the formation
of 1 and 2. But in this case the hydrogen atom has been
transferred toward the former imine nitrogen atom,
thus forming an amine instead with the nitrogen atom
being tetrahedrally surrounded. The lone pair at the
amine nitrogen is coordinating to the iron atom which
metalated the naphthalene ring (Fe2). The apical
Fe(CO)3 group is electronically saturated by a π-allyl
coordination toward C1, C10, and C11.
Figure 3 shows the molecular structure of 4; bond
lengths and angles are summarized in Table 3. 4 is a
tetranuclear iron complex with the iron atoms building
up a chain. Compounds of the same structural type have
been shown to be the thermodynamically most stable
products in the reaction of Ru3(CO)12 with imine ligands
derived from cinnamaldehyde.3a Up to now no iron
complex of this type has been structurally characterized.
Both naphthalene ligands again are metalated by one
iron atom in ortho position with respect to the exocyclic
imine function. In contrast to the compounds mentioned
before, the hydrogen atom being replaced by this meta-
lation reaction is completely removed from the ligand.
F igu r e 3. Molecular structure of 4.
So the iron atom and the ligand build up a five-
membered ring that is absolutely planar and that is
coordinated by another apical iron atom, which now is
bonded to all atoms of the five-membered ring. The iron
atom inside the five-memebered ring shows three
terminal CO ligands, whreas the other iron atom is only
coordinated by one additional terminal CO ligand. Two
of these subunits are linked by a central metal-metal
bond that is slightly longer than the other two iron iron
bonds as well as two bridging CO groups. Although the
molecule in principle shows an internal mirror plane,
there is no crystallographic mirror plane since one of
the cyclohexyl substituents is disordered.
In Figure 4 the molecular structure of 6 is presented;
the numbering scheme has been adopted for 5. The most
important bond lengths and angles are summarized in
Table 4. In principle 5 and 6 show the same structural
features that were already explained for 1 and 2. The
most important difference is the distance between Fe1
and C10, which is 259 pm (5) and 268 pm (6) and
therefore longer than the sum of the covalent radii of
iron and carbon. Corresponding to this, the iron-iron
bond length in 5 and 6 is about 240 pm on average and
thus about 5 pm shorter than was observed for 1 and
2, respectively. It is also worth noticing that there is
selective C-H activation at C1 but never at the second
ortho position with respect to the imine function (C9).
Figure 5 shows the result of the structure analysis of
7; the most important bond lengths and angles are
presented in Table 5. The formation of 7 in principle

Reactivity of Naphthylimines toward Fe2(CO)9
Organometallics, Vol. 18, No. 23, 1999 4849
Ta ble 3. Bon d Len gth s [p m ] a n d An gles [d eg] of 4
Fe1-Fe2
Fe1-C2
C1-C11
Fe2-C2
Fe4-C19
C18-C28
Fe3-C19
252.1(2)
198(1)
144(1)
223.5(8)
198.2(7)
141(1)
Fe2-Fe3
Fe1-N1
C11-N1
Fe2-C11
Fe4-N2
C28-N2
Fe3-C28
258.0(1)
195.6(8)
135(1)
212.7(8)
195.2(6)
136.6(8)
217.3(7)
Fe3-Fe4
C1-C2
Fe2-C1
Fe2-N1
C18-C19
Fe3-C18
Fe3-N2
252.0(1)
142(1)
222.3(7)
207.5(7)
143(1)
224.1(6)
212.5(5)
218.7(7)
Fe1-Fe2-Fe3
Fe1-N1-C11
C1-C2-Fe1
N2-C28-C18
154.16(6)
116.2(6)
113.4(7)
115.1(6)
Fe2-Fe3-Fe4
N1-C11-C1
C19-Fe4-N2
C28-C18-C19
157.48(5)
114.8(8)
81.1(3)
C2-Fe1-N1
C11-C1-C2
Fe4-N2-C28
C18-C19-Fe4
81.4(3)
113.3(7)
116.1(5)
113.2(5)
113.3(6)
Ta ble 4. Bon d Len gth s [p m ] a n d An gles [d eg] of 5 a n d 6
5
Fe1-Fe2
Fe1-N1
C1-C10
240.52(8)
197.9(3)
143.9(5)
Fe1-C1
Fe2-C1
C10-C11
219.2(3)
201.3(4)
149.9(5)
Fe1-C10
Fe2-N1
C11-N1
258.6(5)
198.1(3)
148.9(4)
C1-Fe1-Fe2
C10-Fe1-Fe2
Fe1-Fe2-C1
Fe1-C1-C10
Fe1-N1-Fe2
C1-C10-C11
51.7(1)
70.7(2)
58.7(1)
88.3(2)
74.8(1)
114.0(3)
C1-Fe1-C10
C10-Fe1-N1
Fe1-Fe2-N1
Fe1-C10-C1
Fe1-N1-C11
C10-C11-N1
33.8(2)
60.4(2)
52.58(8)
57.9(2)
104.7(2)
104.0(3)
C1-Fe1-N1
N1-Fe1-Fe2
Fe1-C1-Fe2
Fe1-C10-C11
Fe2-C1-C10
C11-N1-Fe2
74.0(1)
52.62(8)
69.6(1)
80.3(2)
112.8(2)
111.2(2)
6
Fe1-Fe2
Fe1-N1
C1-C10
238.9(2)
198.4(5)
145(1)
Fe1-C1
Fe2-C1
C10-C11
218.7(7)
205.5(9)
149.8(9)
Fe1-C10
Fe2-N1
C11-N1
268(1)
197.6(6)
149.9(9)
C1-Fe1-Fe2
C10-Fe1-Fe2
Fe1-Fe2-C1
Fe1-C1-C10
Fe1-N1-Fe2
C1-C10-C11
53.1(2)
70.3(4)
58.4(2)
92.8(4)
74.2(2)
113.8(7)
C1-Fe1-C10
C10-Fe1-N1
Fe1-Fe2-N1
Fe1-C10-C1
Fe1-N1-C11
C10-C11-N1
32.6(4)
58.8(4)
53.0(2)
54.6(4)
107.0(4)
104.4(5)
C1-Fe1-N1
N1-Fe1-Fe2
Fe1-C1-Fe2
Fe1-C10-C11
Fe2-C1-C10
C11-N1-Fe2
73.5(2)
52.7(2)
68.5(2)
79.1(5)
112.3(5)
112.3(4)
to the second ortho carbon atom of the naphthalene
system. So this is the third possibility of a hydrogen
migration pathway being observed in the reaction of
Fe2(CO)9 with imines of R- or â-naphthylcarbaldehydes.
During the formation of 7 the imine function does not
react at all and the carbon-nitrogen bond length still
is in the range typical for a double bond. The iron atom
bound to C1 is electronically saturated by the coordina-
tion to the lone pair at the imine nitrogen atom. The
apical iron atom is coordinated in a π-allyl fashion to
three carbon atoms of the naphthalene system. The
plane of the allyl system is bent out of the plane of the
remaining aromatic ring (C3 to C8) by 23°
F igu r e 4. Molecular structure of 6.
Figure 6 shows the molecular structure of 9; the
numbering scheme was also adopted for the structure
analysis of 8. The most important bond lengths and
angles are depicted in Table 6. The formation of these
trinuclear iron complexes is only observed in the reac-
tion of â-naphthylcarbaldimine ligands. The reactivity
at the ring bearing the imine group follows the same
pathway as in the reaction leading to 5 and 6. So again
the orthometalation 1,3 hydrogen shift reaction se-
quence is observed leading to the same type of structure
that has already been discussed for 5 and 6. The bond
length between Fe1 and C10 in 8 and 9 is about 20 pm
shorter than in the corresponding dinuclear complexes
5 and 6, and corresponding to this observation, the
iron-iron distance is about 3 pm longer in 8 and 9. The
third Fe(CO)3 group is η4-coordinated to the second ring
of the naphthalene system, as in the well-known (η4-
butadiene)Fe(CO)3 complexes. As a result of this coor-
dination, the plane of the four carbon atoms being
coordinated to the Fe(CO)3 group (C4 to C7) is bent out
F igu r e 5. Molecular structure of 7.
follows a pathway similar to that in the reaction
producing 1, 2, 3, 5, or 6. Again a C-H activation
reaction in ortho position with respect to the imine
moiety and a subsequent hydrogen transfer take place,
but in this case the hydrogen atom is not transferred
to the carbon or nitrogen atom of the imine group but

4850 Organometallics, Vol. 18, No. 23, 1999
Ta ble 5. Bon d Len gth s [p m ] a n d An gles [d eg] of 7
Imhof
Fe1-Fe2
Fe1-C10
C1-C2
C11-N1
C3-C8
265.51(5)
219.6(2)
141.9(3)
127.9(3)
140.0(3)
Fe1-C1
Fe2-C1
C1-C10
C10-C9
C2-C3
195.8(2)
194.8(2)
143.2(3)
151.0(3)
147.4(3)
Fe1-C2
Fe2-N1
C10-C11
C9-C8
217.7(2)
200.2(2)
145.6(3)
152.2(3)
Fe2-Fe1-C2
C2-Fe1-C1
Fe1-Fe2-C1
Fe1-C1-C2
Fe1-C10-C11
C10-C11-N1
C1-C2-C3
77.47(6)
39.69(9)
47.35(7)
78.5(1)
111.3(1)
117.3(2)
121.8(2)
113.5(2)
Fe2-Fe1-C1
C2-Fe1-C10
Fe1-Fe2-N1
Fe1-C1-C10
Fe2-C1-C10
C11-N1-Fe2
C2-C3-C8
47.02(7)
66.11(8)
88.50(6)
79.1(1)
110.3(2)
113.2(2)
120.6(2)
122.7(2)
Fe2-Fe1-C10
C1-Fe1-C10
Fe1-C2-C1
Fe1-C10-C1
C1-C10-C11
N1-Fe2-C1
C3-C8-C9
69.47(6)
39.80(9)
61.8(1)
61.1(1)
112.3(2)
82.58(8)
120.1(2)
113.6(2)
C8-C9-C10
C9-C10-C1
C10-C1-C2
Ta ble 6. Bon d Len gth s [p m ] a n d An gles [d eg] of 8 a n d 9
8
Fe1-Fe2
Fe1-N1
C1-C10
Fe3-C4
Fe3-C7
C5-C6
242.34(4)
196.9(2)
141.9(3)
215.7(2)
215.7(2)
139.8(3)
Fe1-C1
Fe2-C1
C10-C11
Fe3-C5
C3-C4
217.3(2)
199.8(2)
149.8(3)
205.7(2)
147.3(3)
142.0(3)
Fe1-C10
Fe2-N1
C11-N1
Fe3-C6
C4-C5
245.4(2)
198.3(2)
148.0(2)
205.9(2)
142.5(3)
147.0(3)
C6-C7
C7-C8
C1-Fe1-Fe2
C10-Fe1-Fe2
Fe1-Fe2-C1
Fe1-C1-C10
Fe1-N1-Fe2
C1-C10-C11
C4-Fe3-C5
C5-Fe3-C6
Fe3-C4-C5
Fe3-C6-C5
C3-C4-C5
51.18(5)
72.08(4)
57.93(5)
83.4(1)
75.62(5)
115.1(2)
39.44(8)
39.71(9)
66.5(1)
C1-Fe1-C10
C10-Fe1-N1
Fe1-Fe2-N1
Fe1-C10-C1
Fe1-N1-C11
C10-C11-N1
C4-Fe3-C6
C5-Fe3-C7
Fe3-C5-C4
Fe3-C6-C7
C4-C5-C6
35.04(7)
62.16(6)
51.93(4)
61.61(9)
102.1(1)
102.4(1)
68.99(9)
69.20(8)
74.0(1)
C1-Fe1-N1
N1-Fe1-Fe2
Fe1-C1-Fe2
Fe1-C10-C11
Fe2-C1-C10
C11-N1-Fe2
C4-Fe3-C7
C6-Fe3-C7
Fe3-C5-C6
Fe3-C7-C6
C5-C6-C7
74.47(6)
52.45(4)
70.89(6)
82.4(1)
113.2(1)
111.7(1)
75.59(8)
39.28(8)
70.2(1)
70.1(1)
119.9(2)
120.0(2)
74.1(1)
115.6(2)
66.6(1)
116.3(2)
C6-C7-C8
9
Fe1-Fe2
Fe1-N1
C1-C10
Fe3-C4
Fe3-C7
C5-C6
242.86(5)
197.9(2)
142.2(4)
214.5(3)
216.5(3)
141.3(4)
Fe1-C1
Fe2-C1
C10-C11
Fe3-C5
C3-C4
218.7(3)
201.5(3)
150.1(4)
205.1(3)
147.5(4)
141.9(4)
Fe1-C10
Fe2-N1
C11-N1
Fe3-C6
C4-C5
244.6(3)
199.5(2)
148.7(3)
204.2(3)
142.8(4)
147.6(4)
C6-C7
C7-C8
C1-Fe1-Fe2
C10-Fe1-Fe2
Fe1-Fe2-C1
Fe1-C1-C10
Fe1-N1-Fe2
C1-C10-C11
C4-Fe3-C5
C5-Fe3-C6
Fe3-C4-C5
Fe3-C6-C5
C3-C4-C5
51.45(7)
72.75(6)
58.08(7)
82.4(2)
75.35(7)
115.1(2)
39.7(1)
40.4(1)
66.6(2)
70.1(2)
119.2(2)
119.2(2)
C1-Fe1-C10
C10-Fe1-N1
Fe1-Fe2-N1
Fe1-C10-C1
Fe1-N1-C11
C10-C11-N1
C4-Fe3-C6
C5-Fe3-C7
Fe3-C5-C4
Fe3-C6-C7
C4-C5-C6
35.19(9)
62.48(9)
52.02(6)
62.4(1)
101.6(2)
102.4(2)
70.1(1)
69.5(1)
73.7(2)
75.1(2)
115.7(3)
C1-Fe1-N1
N1-Fe1-Fe2
Fe1-C1-Fe2
Fe1-C10-C11
Fe2-C1-C10
C11-N1-Fe2
C4-Fe3-C7
C6-Fe3-C7
Fe3-C5-C6
Fe3-C7-C6
C5-C6-C7
74.52(9)
52.63(6)
70.47(8)
82.8(2)
113.4(2)
112.0(2)
76.2(1)
39.3(1)
69.5(2)
65.6(2)
116.2(3)
C6-C7-C8
derivatives.11 There is only one example of a benzene
derivative described, namely, the Fe(CO)3 complex of
1,2,3,4-tetramethyl-5,6-bis(trifluoromethyl)benzene, which
was formed by photolysis of (η4-C4Me4)Fe(CO)3 in the
presence of hexafluorobutyne.12 All other compounds
that were published before are very electron poor
aromatic compounds such as derivatives of 1,4-di-
boranaphthalene or 9,10-diboraanthracene.13
(11) (a) Herbstein, F. H.; Reisner, M. G. Acta Crystallogr., Sect. B
1977, 33, 3304-3317. (b) Schaufele, H.; Hu, D.; Pritzkow, H.; Zenneck,
U. Organometallics 1989, 8, 396-401. (c) Brodt, C.; Niu, S.; Pritzkow,
H.; Stephan, M.; Zenneck, U. J . Organomet. Chem. 1993, 459, 283-
291. (d) Petrel, T. A.; Stephan, J . M.; McDaniel, K. F.; McMills, M. C.;
Rheingold, A. L.; Yap, G. P. A. J . Org. Chem. 1996, 61, 4188-4189.
(e) Bennett, M. A.; Lu, Z.; Wang, X.; Bown, M.; Hockless, D. C. R. J .
Am. Chem. Soc. 1998, 120, 10409.
F igu r e 6. Molecular structure of 9.
of the plane of the other naphthalene carbon atoms (C1,
C2, C3, C8, C9, C10) by 28° (8) or 34° (9), respectively.
There are only a few structurally characterized com-
pounds in which an aromatic π-system is η4-coordinated
to an Fe(CO)3 group including naphthalene and indene
(12) Bond, A.; Bottrill, M.; Green, M.; Welch, A. J . J . Chem. Soc.,
Dalton Trans. 1977, 2372-2381.

Reactivity of Naphthylimines toward Fe2(CO)9
Organometallics, Vol. 18, No. 23, 1999 4851
Ta ble 7. Bon d Len gth s [p m ] a n d An gles [d eg] of 10
Fe1-C1
Fe1-N1
C11-N1
217.6(2)
206.2(2)
135.5(3)
Fe1-C2
C1-C2
212.4(2)
143.8(3)
Fe1-C11
C2-C11
208.8(2)
142.6(3)
C1-Fe1-C2
C2-Fe1-C11
Fe1-C1-C2
Fe1-C11-C2
C1-C2-C11
39.05(9)
39.55(9)
68.5(1)
71.6(1)
116.5(2)
C1-Fe1-C11
C2-Fe1-N1
Fe1-C2-C1
Fe1-C11-N1
C2-C11-N1
69.61(9)
68.56(8)
72.4(1)
69.9(1)
116.0(2)
C1-Fe1-N1
C11-Fe1-N1
Fe1-C2-C11
Fe1-N1-C11
77.79(8)
38.10(8)
68.9(1)
72.0(1)
the former imine carbon atom at δ ) 4.20, which is now
part of a π-allyl system and is thus shifted to higher
field by coordination to the iron atom. This allyl moiety
also gives rise to characteristic signals in the 13C NMR
spectrum, δ ) 61.9, 68.5, and 100.6, whereas the other
carbon atoms are observed at expected chemical shifts.
The spectroscopical properties of 4 are identical with
those of the corresponding ruthenium complexes. NMR
measurements at 70 °C in toluene-d8 have shown that
there is no thermally induced interconversion of the
isomeric compounds 2 and 3 into each other.
F igu r e 7. Molecular structure of 10.
1
The H NMR spectra of 5 and 6 also show the signals
Figure 7 presents the molecular structure of 10; the
most important bond lengths and angles are shown in
Table 7. 10 is the first example of a (η4-azadiene)Fe-
(CO)3 complex in which the C-C double bond is part of
an aromatic system. Up to now only azadiene complexes
with ligands derived from acyclic R,â-unsaturated al-
dehydes have been published.5 The coordination of the
iron atom is slightly unsymmetrical. The bond lengths
of iron to the imine nitrogen and the imine carbon atom
are of about the same value, whereas the two iron-
carbon bond lengths to the naphthalene double bond are
significantly longer. The C-C and C-N double bonds
of the azadiene are elongated by coordination to the
metal, and the central C-C bond is shortened, as was
shown to be typical for complexes of this type.5 Recently
we were able to show by means of extended Hu¨ckel
calculations on (η4-azadiene)Fe(CO)3 complexes that
these compounds stabilize themselves by bending of the
hydrogen at the C-terminus of the azadiene chain (C1
in 10) out of the plane of the azadiene system itself. By
this process the overlap of the MOs at C1 and Fe1 is
increased.5k The same observation can be made in the
molecular structure of 10 since the distance of H1 with
respect to the plane through N1, C11, C2, and C2 is 54.2
pm.
representing the methylene groups at δ ) 4.30 (5) and
4.66 (6), respectively, as one characteristic feature.
Besides this, the hydrogen atoms at C2 (see Figure 4)
are shifted to lower field and give rise to singlets at δ )
8.74 (5) and 8.72 (6). The corresponding carbon reso-
nances of the methylene group both are observed at δ
) 76.0, whereas the signals of the naphthalene system,
the organic substituents at nitrogen, and the CO ligands
show signals in the expected regions. The NMR spectra
of 7 also show characteristic resonances for the meth-
ylene group, which in this case was formed at C9 (see
Figure 5). The two hydrogen atoms at C9 are diaste-
reotopic and thus give rise to a AB pattern of the signals
with a coupling constant of 21.3 Hz. The proton at C2,
which is part of a π-allyl system, is observed as a singlet
at δ ) 5.90, as is the resonance representing the
unreacted imine hydrogen at δ ) 8.17. The other
hydrogen atoms show signals at expected values. In the
13C NMR spectrum of 7 the methylene group occurs in
the range of about δ ) 30; the carbon atoms of the allyl
system show signals at about δ ) 80 for the two outer
carbon atoms and in the aromatic region for the central
carbon atom. The resonance of the imine carbon atom
at δ ) 179.0 is observed at a 20 pm lower shift compared
to the free ligand. The molecular structure of 8 and 9 is
closely related to the structures of 5 and 6 (see Figures
4 and 6). In 8 and 9 the same C-H activation hydrogen
shift reaction sequence has taken place ortho to the
imine function of the free ligand. The second ring of the
naphthalene system is coordinating another Fe(CO)3
moiety. The introduction of this third Fe(CO)3 group in
8 and 9 in contrast to the spectra of 5 and 6 now leads
to the observation of diastereotopicity at the methylene
group (C11, Figure 6). Since it is not reasonable that
the Fe2(CO)6 moiety is affected by the new Fe(CO)3
group concerning its fluxionality the reason for the
protons at C11 to become diastereotopic must be the
bending of the naphthalene system. So the methylene
groups in 8 and 9 show an AB spin pattern with a
coupling constant of about 12 Hz. The two remaining
hydrogen atoms at the first ring of the naphthalene
system at C2 and C9 (see Figure 6) give rise to singlets
at δ ) 6.58 and 7.21, respectively, for 8. In the NMR
NMR Sp ectr oscop y
The NMR spectra of 1 and 2 as expected show
properties closely related to those of other dinuclear iron
complexes derived from imines of monocyclic aromatic
ligands.6 So the most significant feature is the reso-
nances representing the methylene group that is formed
during the reaction and is observed at δ ) 4.20 (1) or δ
) 4.68 (2), respectively, in the hydrogen NMR and at
about δ ) 74 for both compounds in the carbon NMR
spectra. The signals of the coordinated naphthalene
system are also very similar to those reported for
benzaldimine complexes (see Experimental Part).6d The
1H NMR spectrum of 3 beneath the naphthalene protons
shows the NH group at δ ) 5.26 and the hydrogen at
(13) (a) Schulz, H.; Pritzkow, H.; Siebert, W. Chem. Ber. 1991, 124,
2203-2207. (b) Schulz, H.; Pritzkow, H.; Siebert, W. Chem. Ber. 1992,
125, 987-991.

4852 Organometallics, Vol. 18, No. 23, 1999
Ta ble 8. Cr ysta l a n d In ten sity Da ta for th e Com p ou n d s 1-4
Imhof
1
2
3
4
formula
C
23H19NO6Fe2
C23H13NO6Fe2
511.04
Mo KR
graphite
293
C23H13NO6Fe2
511.04
Mo KR
graphite
213
orange
0.2 × 0.2 × 0.1
10.245(3)
13.757(3)
14.906(3)
92.88(1)
91.86(2)
91.00(1)
2096.7(9)
4
C44H34N2O10Fe4
1021.21
Mo KR
mol weight [g mol-1
radiation
monochromator
temperature [K]
crystal color
crystal size
a [Å]
]
517.09
Mo KR
graphite
213
graphite
183
red
red
red-brown
0.4 × 0.3 × 0.3
10.6109(7)
13.8439(9)
17.298(1)
97.284(5)
102.698(4)
90.181(5)
2457.5(3)
2
0.2 × 0.2 × 0.03
17.261(3)
8.335(2)
15.213(2)
90
0.4 × 0.3 × 0.1
12.143(3)
12.981(4)
16.142(5)
113.10(1)
106.20(2)
95.20(2)
2189(1)
4
b [Å]
c [Å]
R [deg]
â [deg]
90
90
γ [deg]
volume [Å3]
Z
2188.7(7)
4
F(000)
F
1056
1.569
orthorhombic
Pca21
1.365
1032
1.551
triclinic
P1h
1.364
1032
1.619
triclinic
P1h
1.428
1044
1.380
triclinic
P1h
1.212
2.43-23.31
æ
calc [g cm-3
]
crystal system
space group
abs coeff [mm-1
θ limit
]
2.36-27.99
1.46-30.64
1.37-36.47
scan mode
θ-2θ
θ-2θ
θ-2θ
scan speed [deg min-1
no. of reflns measd
no. of indep reflns
]
3-60
3-60
3-60
3455
9087
7412
6520
6520
2876
8312
6972
R(int)
0.0505
2041
300
0.0193
5717
597
0.0349
4979
681
0.0000
5162
629
2
2
no. of obs reflns Fo > 2σ(Fo
no. of params
)
GOOF
R1
wR2
1.039
0.967
1.017
1.154
0.0738
0.1585
1.142
0.0575
0.1079
0.564
0.0471
0.1123
0.567
0.0464
0.0972
0.449
final diff map electron
density [e Å-3
]
solvents. Chromatography was done using silica gel 60 and
silanized silica gel 60, 70-230 mesh ASTM (Merck), which were
dried at 10-2 bar (103 Pa) for 2 days before use. Fe2(CO)9 was
prepared from Fe(CO)5 (Aldrich) by irradiation in acetic acid.14
Infrared spectra were recorded on a Perkin-Elmer FT-IR
System 2000 using 0.2 mm KBr cuvettes. NMR spectra were
recorded on a Bruker AC 200 spectrometer (1H, 200 MHz with
SiMe4 as internal standard; 13C, 50.32 MHz with CDCl3 as
internal standard); 1H, 13C, and HMQC spectra of 9 and 10
on a Bruker DRX 400 spectrometer (1H, 400 MHz; 13C, 100.62
MHz with CDCl3 as internal standard). Mass spectra were
recorded on a Finnigan MAT SSQ 710 instrument. Elemental
analyses were carried out at the laboratory of the Institute of
Organic Chemistry and Macromolecular Chemistry of the
Friedrich-Schiller-University J ena.
X-r a y Cr ysta llogr a p h ic Stu d ies. Structure determina-
tions of 1, 2, 3, 5, and 6 were carried out on a Siemens P4
diffractometer. Structure determinations of 4, 7, 8, 9, and 10
were carried out using a Enraf Nonius Kappa CCD diffracto-
meter, crystal detector distance 25 mm, 180 frames. In both
cases graphite-monochromated Mo KR radiation was used. The
crystals were mounted in a stream of cold nitrogen. Data were
corrected for Lorentz and polarization effects but not for
absorption. The structures were solved by direct methods and
refined by full-matrix least-squares techniques against F2
using the programs SHELXS86 and SHELXL93.15 Computa-
tions of the structures were done with the program XPMA,16
and the molecular illustrations were drawn using the program
XP.17 The crystal and intensity data are given in Tables 8 and
9. Additional material on the structure analyses is available
from the Cambridge Crystallographic Data Centre by men-
tioning the deposition numbers 117389 (1), 117390 (2), 117391
spectrum of 9 only the singlet at δ ) 6.69 representing
the proton at C9 can be identified since the resonance
of the hydrogen atom at C2 is overlapped by the
multiplet structure of the nitrogen-bound phenyl group.
The hydrogen atoms at the second ring of the naphtha-
lene system which is now η4-coordinated to the third
Fe(CO)3 moiety are shifted to higher field compared to
the free ligand. Since this “butadiene” subunit is un-
symmetrically substituted at the outer carbon atoms,
all four hydrogen atoms are different. The inner hydro-
gen atoms at C5 and C6 (see Figure 6) show a nearly
identical chemical shift and thus give rise to multiplet
structures in the hydrogen NMR spectra of both 8 and
9 at about δ ) 6.3. The signals for the hydrogen atoms
at C4 and C7 each show well-separated doublets of
doublets at about δ ) 3.5-3.6. In the 13C NMR spectra
of 8 and 9 the signals of the methylene groups are
observed at δ ) 74.0 (8) and 76. 4 (9), respectively. Most
typical for these compounds are the resonances of the
four carbon atoms coordinated to the third Fe(CO)3
group. For the outer carbon atoms (C4 and C7, see
Figure 6) two signals at about δ ) 62 are observed for
both 8 and 9, whereas the inner carbon atoms of this
“butadiene” subunit give rise to two singlets at δ ) 67.
In the NMR spectra of 10 the hydrogen and carbon
resonances of the “azadiene” subunit coordinating the
Fe(CO)3 group as expected are shifted to higher field
compared to the spectra of the free ligand. Their
chemical shifts correspond very well with those of the
related (η4-azadiene)Fe(CO)3 complexes with ligands of
the cinnamaldehyde type.5
(14) Brauer, G. Handbuch der Pra¨p. Anorg. Chemie, 8th ed.; VCH:
Weinheim, 1968; Part C, No. 1, p 19.
(15) (a) Sheldrick, G. SHELXS-86; Universita¨t Go¨ttingen, 1986. (b)
Sheldrick, G. SHELXL-93; Universita¨t Go¨ttingen, 1993.
(16) Zsolnai, L.; Huttner, G. XPMA; Universita¨t Heidelberg, 1996.
(17) XP-Interactive Molecular Graphics, Vers. 4.2; Siemens Analyti-
cal Xray Inst. Inc., 1990.
Exp er im en ta l P a r t
Gen er a l P r oced u r es. All procedures were carried out
under an argon atmosphere in anhydrous, freshly distilled

Reactivity of Naphthylimines toward Fe2(CO)9
Organometallics, Vol. 18, No. 23, 1999 4853
Ta ble 9. Cr ysta l a n d In ten sity Da ta for th e Com p ou n d s 5-10
5
6
7
8
9
10
formula
C
23H19NO6Fe2
C23H13NO6Fe2
511.04
Mo KR
graphite
213
purple
0.4 × 0.2 × 0.02
7.964(5)
10.472(2)
13.658(3)
75.18(1)
74.68(3)
82.65(3)
1059.8(7)
2
C23H19NO6Fe2
517.09
Mo KR
graphite
183
C26H19NO9Fe3
656.97
Mo KR
graphite
183
C26H13NO9Fe3
650.92
Mo KR
graphite
183
C20H13NO3Fe
371.16
Mo KR
graphite
183
orange
0.8 × 0.3 × 0.1
11.283(2)
16.930(3)
9.323(2)
90
mol weight [g mol-1
radiation
monochromator
temperature [K]
crystal color
crystal size
a [Å]
]
517.09
Mo KR
graphite
293
purple
0.2 × 0.2 × 0.2
8.779(1)
24.927(2)
10.046(2)
90
red
orange
orange
0.2 × 0.2 × 0.2
8.1509(4)
10.2714(5)
13.6492(6)
80.111(3)
89.565(3)
77.561(3)
1098.88(9)
2
0.3 × 0.2 × 0.05
12.8617(4)
14.8351(5)
14.4385(4)
90
108.781(2)
90
2608.2(1)
4
0.2 × 0.2 × 0.08
8.2177(4)
10.7951(5)
14.7951(5)
80.207(3)
77.630(3)
80.602(2)
1252.32(9)
2
b [Å]
c [Å]
R [deg]
â [deg]
92.93(1)
90
2195.5(5)
4
110.37(3)
90
1669.5(6)
4
γ [deg]
volume [Å3]
Z
F(000)
F
1056
1.564
monoclinic
P21/n
1.361
516
1.601
triclinic
P1h
1.409
528
1.563
triclinic
P1h
1.360
3.01-23.26
æ
1328
1.673
monoclinic
P21/n
1.701
3.12-23.28
æ
652
1.726
triclinic
P1h
1.771
2.68-23.30
æ
760
1.477
monoclinic
P21/c
0.921
2.73-23.27
æ
calc [g cm-3
]
crystal system
space group
abs coeff [mm-1
θ limit
]
1.63-27.00
1.59-26.67
scan mode
θ-2θ
θ-2θ
scan speed [deg min-1
no. of reflns measd
no. of indep reflns
R(int)
]
3-60
3-60
5997
5136
2974
2974
0.0000
2682
6910
3737
0.0225
3499
3366
3366
0.0000
3174
4379
2377
0.0439
2198
4796
0.0423
3028
4166
0.0438
2515
no. of obs reflns
2
2
Fo > 2σ(Fo
)
no. of params
GOOF
R1
365
339
369
428
404
278
1.023
0.0454
0.0801
0.295
1.016
0.0622
0.1439
0.897
1.026
0.0309
0.0690
0.250
1.017
0.0224
0.0698
0.272
1.091
0.0260
0.0929
0.358
1.041
0.0343
0.0892
0.300
wR2
final diff map electron
density [e Å-3
]
(3), 117392 (4), 117393 (5), 117394 (6), 117395 (7), 117396 (8),
117397 (9), 117398 (10), the author, and the journal citation.
P r ep a r a tion of th e Im in e Liga n d s. The imines are
prepared by reacting 2 g (12.8 mmol) of R- or â-naphthylcarb-
aldehyde with an equimolar amount of the corresponding
amine (1.27 g cyclohexylamine, 1.19 g aniline). The reaction
is carried out in 20 mL of ethanol together with a catalytic
amount of p-toluenesulfonic acid and monitored by GC. After
the reaction is completed the imines from R-naphthylcarbal-
237 (M+, 91), 208 (C15H14N+, 50), 194 (C14H12N+, 78), 180
(C13H10N+, 39), 167 (C12H9N+, 23), 154 (C11H8N+, 100), 139
(C10H5N+, 41), 127 (C9H5N+, C10H7+, 42), 83 (C6H11+, 18), 55
(C4H7+, 29), 41 (C3H5+, 25); 1H NMR (CDCl3, 298 K) [ppm]
1.25-1.90 (m, 11H, CH2), 3.22-3.32 (m, 1H, CH), 7.47-7.52
(m, 2H, CH), 7.81-8.09 (m, 3H, CH), 8.42 (s, 1H, NdCH); 13
C
NMR (CDCl3, 298 K) [ppm] 24.7 (CH2), 25.6 (CH2), 34.3 (CH2),
69.7 (CH), 124.0 (CH), 126.1 (CH), 126.7 (CH), 127.6 (CH),
128.1 (CH), 128.3 (CH), 129.3 (CH), 133.0 (C), 134.2 (C), 134.4
(C), 158.3 (NdCH).
dehyde are distilled to yield yellow oily products (R ) C6H11
:
bp 127 °C, 5.2 × 10-5 Torr, yield 2.82 g, 93%. R ) C6H5: bp
132 °C, 2.9 × 10-5 Torr, yield 2.59 g, 86%), whereas the imines
from â-naphthylcarbaldehyde crystallize during the reaction.
The crude products are collected and recrystallized from
ethanol (R ) C6H11: mp 120 °C, yield 2.67 g, 88%. R ) C6H5:
mp 92 °C, yield 1.95 g, 65%).
â-Na p h th ylid en e-N-p h en ylim in e: MS (EI) m/z (%) 231
(M+, 100), 230 (M+ - H, 86), 202 (C15H8N+, 7), 153 (C11H7N+,
3), 139 (C10H5N+, 7), 127 (C9H5N+, 22), 115 (C8H5N+, 24), 101
(C7H3N+, 8), 89 (C7H5+, 3), 77 (C6H5+, 62), 63 (C5H3+, 3), 51
(C4H3+, 15); 1H NMR (CDCl3, 298 K) [ppm] 7.24-7.60 (m, 7H,
CH), 7.86-7.95 (m, 3H, CH), 8.18-8.22 (m, 2H, CH), 8.61 (s,
1H, NdCH); 13C NMR (CDCl3, 298 K) [ppm] 120.7 (CH), 123.7
(CH), 125.7 (CH), 126.4 (CH), 127.3 (CH), 127.7 (CH), 128.4
(CH), 128.5 (CH), 128.9 (CH), 130.9 (CH), 132.9 (C), 133.8 (C),
134.8 (C), 151.9 (C), 160.0 (NdCH).
r-Na p h th ylid en e-N-cycloh exylim in e: MS (EI) m/z (%)
237 (M+, 100), 208 (C15H14N+, 18), 194 (C14H12N+, 47), 180
(C13H10N+, 28), 166 (C12H8N+, 18), 154 (C11H8N+, 92), 141
(C10H7N+, 21), 127 (C9H5N+, C10H7+, 26), 83 (C6H11+, 10), 55
(C4H7+, 17), 41 (C3H5+, 15); H NMR (in CDCl3, 298 K) [ppm]
Tr ea tm en t of r-Na p h th ylca r ba ld im in es w ith F e2(CO)9.
A 500 mg sample of Fe2(CO)9 (1.37 mmol) is reacted with 1.64
mmol of the respective R-naphthylcarbaldimine (R ) C6H11,
1
1.13-1.81 (m, 10H, CH2), 3.23-3.37 (m, 1H, CH), 7.45-7.60
3
(m, 3H, CH), 7.80-8.02 (m, 3H, CH), 8.87 (d, J HH ) 8.38 Hz,
1H, CH), 8.97 (s, 1H, NdCH); 13C NMR (in CDCl3, 298 K)
[ppm] 24.8 (CH2), 25.8 (CH2), 34.6 (CH2), 70.8 (CH), 124.4 (CH),
125.2 (CH), 125.9 (CH), 126.9 (CH), 128.3 (CH), 128.5 (CH),
130.5 (CH), 131.4 (C), 132.2 (C), 133.9 (C), 157.9 (CH).
r-Na p h th ylid en e-N-p h en ylim in e: MS (EI) m/z (%) 231
(M+, 70), 230 (M+ - H, 100), 202 (C15H8N+, 5), 154 (C11H8N+,
5), 127 (C9H5N+, 24), 114 (C8H4N+, 8), 101 (C7H3N+, 4), 77
(C6H5+, 29), 63 (C5H3+, 3), 51 (C4H3+, 10); 1H NMR (CDCl3,
298 K) [ppm] 7.24-8.27 (m, 11H, CH), 9.13-9.19 (m, 2H, CH,
NdCH); 13C NMR (CDCl3, 298 K), [ppm] 120.8 (CH), 124.2
(CH), 125.1 (CH), 125.8 (CH), 126.0 (CH), 127.3 (CH), 128.6
(CH), 129.1 (CH), 129.8 (CH), 131.3 (C), 131.7 (CH, C), 133.7
(C), 152.5 (C), 159.8 (NdCH).
380 mg; R ) C6H5, 370 mg) in 30 mL of n-heptane at 50 °C.
After 45 min all of the starting material is dissolved and the
color of the solution has changed from light yellow to deep red.
The volatile material is evaporated in vacuo, and the oily
residue is dissolved in 10 mL of CH2Cl2. A 2 g portion of
silanized silica gel is added, and the solvent is removed in
vacuo. The product mixture is chromatographed on silica gel
using mixtures of light petroleum (bp 40-60 °C) and CH2Cl2.
In both reactions at first a small amount of Fe3(CO)12 is eluted.
In the reaction of the R-naphthylcarbaldimine with R ) C6H11
392 mg (54.7%) of 1 is obtained using a mixture of light
petroleum/CH2Cl2 (6:1), and with a mixture of light petroleum/
CH2Cl2 (1:1) 65 mg (5%) of 4 is observed. Using the R-naph-
thylcarbaldimine with R ) C6H5 210 mg (30%) of 2 is obtained
â-Na p h th ylid en e-N-cycloh exylim in e: MS (EI) m/z (%)

4854 Organometallics, Vol. 18, No. 23, 1999
Imhof
with a mixture of light petroleum/CH2Cl2 (20:1), and increasing
the ratio to 2:1 164 mg (23%) of 3 is collected. 1 and 2 are
intensively red colored, whereas 3 is orange and 4 shows a
red-brown color. 1, 2, and 3 are recrystallized from mixtures
of light petroleum/CH2Cl2 at -20 °C. 4 is recrystallized from
light petroleum/toluene (3:1) at -20 °C.
(toluene-d8, 298 K) [ppm] 25.8 (CH2), 25.9 (CH2), 26.8 (CH2),
26.9 (CH2), 30.3 (CH2), 35.5 (CH2), 40.3 (CH2), 71.1 (CH), 71.4
(CH), 116.1 (C), 124.4 (CH), 125.4 (CH), 127.0 (CH), 129.7 (C),
130.2 (CH), 133.8 (CH), 136.9 (CH), 140.0 (CH), 144.1 (C),
163.8 (C), no signals of CO ligands have been observed. Anal.
Calcd for C44H34N2O10Fe4: C, 54.25; H, 3.52; N, 2.88. Found:
C, 55.08; H, 3.76; N, 2.51.
Tr ea tm en t of â-Na p h th ylca r ba ld im in es w ith F e2(CO)9.
A 500 mg sample of Fe2(CO)9 (1.37 mmol) is reacted with 1.64
mmol of the respective â-naphthylcarbaldimine (R ) C6H11,
MS a n d Sp ectr oscop ica l Da ta of 1: MS (EI) m/z (%) 517
(M+, 7), 489 (M+ - CO, 4), 461 (M+ - 2 CO, 16), 433 (M+ - 3
CO, 7), 405 (M+ - 4 CO, 13), 377 (M+ - 5 CO, 63), 349 (M+
-
6 CO, 62), 287 (C17H13NFe+, 19), 266 (C15H16NFe+, 18), 240
(C13H14NFe+, 21), 211 (C15H17N+, 25), 198 (C14H16N+, 60), 188
(C13H18N+, 32), 185 (C13H15N+, 28), 175 (C12H17N+, 54), 150
(C10H16N+, 44), 141 (C11H9+, 87), 112 (Fe2+, 84), 97 (C6H11N+,
17), 83 (C6H11+, 15), 56 (Fe+, 100), 41 (C3H5+, 13); IR (CH2Cl2,
380 mg; R ) C6H5, 370 mg) in 30 mL of n-heptane at 50 °C.
After 1 h all of the starting material is dissolved and the color
of the solution has changed from light yellow to deep red. The
volatile material is evaporated in vacuo, and the oily residue
is dissolved in 10 mL of CH2Cl2. A 2 g portion of silanized silica
gel is added, and the solvent is removed in vacuo. The product
mixture is chromatographed on silica gel using mixtures of
light petroleum (bp 40-60 °C) and CH2Cl2. In both reactions
at first a small amount of Fe3(CO)12 is eluted. In the reaction
of the â-naphthylcarbaldimine with R ) C6H11 200 mg (28%)
of 5 is obtained using pure light as the eluent, with a mixture
of light petroleum/CH2Cl2 (10:1) 150 mg (17%) of 8 is observed,
and the use of a mixture of light petroleum/CH2Cl2 (3:1) leads
to the isolation of 144 mg (20%) of 7. Using the â-naphthyl-
carbaldimine with R ) C6H5 320 mg (46%) of 6 is obtained
with a mixture of light petroleum/CH2Cl2 (10:1), the use of a
mixture of light petroleum/CH2Cl2 (5:1) leads to the isolation
of 40 mg (4%) of 9, and increasing the ratio to 3:1 25 mg (5%)
of 10 are collected. 5 and 6 both are of purple color, 7 is of
red-brown color, and 8 and 9 both are orange colored, as is
10. All compounds are recrystallized from mixtures of light
petroleum/CH2Cl2 at -20 °C.
MS a n d Sp ectr oscop ica l Da ta of 5: MS (EI) m/z (%) 517
(M+, 5), 489 (M+ - CO, 1), 461 (M+ - 2 CO, 26), 433 (M+ - 3
CO, 11), 405 (M+ - 4 CO, 26), 377 (M+ - 5 CO, 65), 349 (M+
- 6 CO, 100), 293 (C17H19NFe+, 3), 287 (C17H13NFe+, 25), 265
(C15H14NFe+, 17), 198 (C14H16N+, 24), 188 (C13H18N+, 21), 141
(C11H9+, 24), 112 (Fe2+, 20), 97 (C6H11N+, 5), 56 (Fe+, 17); IR
(CH2Cl2, 298 K) [cm-1] 2058 (m), 2020 (vs), 1976 (s, br); 1H
NMR (CDCl3, 298 K) [ppm] 0.84-2.15 (m, 10H, CH2), 2.55-
2.76 (m, 1H, CH), 4.30 (s, 2H, CH2), 7.42-7.82 (m, 5H, CH),
8.74 (s, 1H, CH); 13C NMR (CDCl3, 298 K) [ppm] 26.2 (CH2),
26.4 (CH2), 35.9 (CH2), 64.8 (CH), 76.0 (CH2), 110.6 (C), 120.2
(CH), 126.4 (CH), 127.8 (CH), 128.4 (CH), 129.2 (C), 132.7 (C),
136.2 (C), 145.3 (CH), 159.9 (CH), 210.4 (CO). Anal. Calcd for
C23H19NO6Fe2: C, 53.42; H, 3.70; N, 2.71. Found: C, 53.75;
H, 4.08; N, 2.74.
1
298 K) [cm-1] 2061 (m), 2024 (vs), 1981 (s, br), 1964 (sh); H
NMR (CDCl3, 298 K) [ppm] 1.01-1.87 (m, 10H, CH2), 2.19-
3
2.26 (m, 1H, CH), 4.20 (s, 2H, CH2), 7.26 (d, J HH ) 8.9 Hz,
1H, CH), 7.50-7.58 (m, 2H, CH), 7.68-7.76 (m, 1H, CH),
7.87-7.96 (m, 2H, CH); 13C NMR (CDCl3, 298 K) [ppm] 26.1
(CH2), 26.2 (CH2), 35.4 (CH2), 62.3 (CH), 74.1 (CH2), 107.6 (C),
124.8 (CH), 125.7 (CH), 127.4 (CH), 127.5 (CH), 129.2 (CH),
133.5 (C), 134.2 (C), 142.7 (CH), 153.8 (C), 210.5 (CO). Anal.
Calcd for C23H19NO6Fe2: C, 53.42; H, 3.70; N, 2.71. Found:
C, 53.33; H, 3.93; N, 2.77.
MS a n d Sp ectr oscop ica l Da ta of 2: MS (EI) m/z (%) 511
(M+, 12), 483 (M+ - CO, 8), 455 (M+ - 2 CO, 27), 427 (M+
-
3 CO, 8), 399 (M+ - 4 CO, 28), 371 (M+ - 5 CO, 67), 343 (M+
- 6 CO, 100), 287 (C17H13NFe+, 61), 260 (C15H10NFe+, 9), 230
(C17H12N+, 14), 215 (C16H9N+, 21), 202 (C15H8N+, 21), 183
(C13H13N+, 19), 171 (C12H13N+, 69), 139 (C11H7+, 12), 112 (Fe2
,
+
14), 77 (C6H5+, 7), 56 (Fe+, 38); IR (CH2Cl2, 298 K) [cm-1] 2066
(m), 2030 (vs), 1989 (s, br), 1974 (sh); 1H NMR (CDCl3, 298 K)
[ppm] 4.68 (s, 2H, CH2), 7.04-7.14 (m, 3H, CH), 7.20-7.34
(m, 3H, CH), 7.48-7.60 (m, 2H, CH), 7.74-7.79 (m, 1H, CH),
7.83-7.92 (m, 2H, CH); 13C NMR (CDCl3, 298 K) [ppm] 73.6
(CH2), 105.5 (C), 122.8 (CH), 124.6 (CH), 125.6 (CH), 126.1
(CH), 127.4 (CH), 127.6 (CH), 129.0 (CH), 129.2 (CH), 133.4
(C), 134.8 (C), 142.5 (CH), 156.2 (C), 158.8, (C), 210.1 (CO).
Anal. Calcd for C23H23NO6Fe2: C, 54.06; H, 2.56; N, 2.74.
Found: C, 54.09; H, 2.64; N, 2.88.
MS a n d Sp ectr oscop ica l Da ta of 3: MS (EI) m/z (%) 511
(M+, 12), 483 (M+ - CO, 9), 455 (M+ - 2 CO, 10), 427 (M+
-
3 CO, 12), 399 (M+ - 4 CO, 29), 371 (M+ - 5 CO, 35), 343 (M+
- 6 CO, 52), 287 (C17H13NFe+, 23), 230 (C17H12N+, 86), 216
(C16H10N+, 17), 202 (C15H8N+, 22), 171 (C12H13N+, 24), 167
(C12H9N+, 44), 149 (C11H3N+, 100), 128 (C9H6N+, 25), 112 (Fe2
,
+
31), 83 (C5H9N+, 24), 77 (C6H5+, 30), 71 (C4H9N+, 57), 57 (FeH+,
88), 56 (Fe+, 63) 43 (C3H7+, 55); IR (CH2Cl2, 298 K) [cm-1] 2062
(m), 2019 (vs), 1983 (s, br), 1958 (sh); 1H NMR (CDCl3, 298 K)
[ppm] 4.20 (s, 1H, CH), 5.26 (s, 1H, NH), 6.53-6.56 (m, 1H,
CH), 6.87-7.03 (m, 3H, CH), 7.48-7.64 (m, 4H, CH), 7.72-
7.92 (m, 2H, CH), 8.23-8.32 (m, 1H, CH); 13C NMR (CDCl3,
298 K) [ppm] 61.9 (CH), 68.5 (C), 100.6 (C), 117.7 (CH), 122.5
(CH), 125.5 (CH), 125.9 (CH), 127.5 (CH), 128.8 (CH), 129.5
(CH), 133.1 (C), 134.5 (C), 142.4 (CH), 152.0 (CH), 157.8, (C),
212.8 (CO). Anal. Calcd for C23H23NO6Fe2: C, 54.06; H, 2.56;
N, 2.74. Found: C, 54.06; H, 2.54; N, 3.09.
MS a n d Sp ectr oscop ica l Da ta of 6: MS (EI) m/z (%) 511
(M+, 6), 483 (M+ - CO, 5), 455 (M+ - 2 CO, 31), 427 (M+ - 3
CO, 10), 399 (M+ - 4 CO, 25), 371 (M+ - 5 CO, 45), 343 (M+
- 6 CO, 100), 315 (M+ - 5CO - Fe, 2), 287 (C17H13NFe+, 68),
260 (C15H10NFe+, 7), 230 (C17H12N+, 19), 215 (C16H9N+, 11),
202 (C15H8N+, 18), 182 (C13H12N+, 12), 171 (C12H13N+, 49), 139
(C11H7+, 11), 112 (Fe2+, 13), 77 (C6H5+, 9), 56 (Fe+, 33); IR (CH2-
1
Cl2, 298 K) [cm-1] 2064 (m), 2025 (vs), 1984 (s, br); H NMR
(CDCl3, 298 K) [ppm] 4.66 (s, 2H, CH2), 7.18-7.85 (m, 10H,
CH), 8.72 (s, 1H, CH); 13C NMR (CDCl3, 298 K) [ppm] 76.0
(CH2), 109.5 (C), 122.7 (CH), 124.4 (CH), 125.6 (CH), 126.8
(CH), 127.5 (CH), 127.9 (CH), 129.0 (CH), 131.9 (C), 133.7
(CH), 135.5 (C), 137.2 (C), 157.3 (CH), 159.8 (C), 210.3 (CO).
Anal. Calcd for C23H23NO6Fe2: C, 54.06; H, 2.56; N, 2.74.
Found: C, 54.40; H, 2.71; N, 2.74.
MS a n d Sp ectr oscop ica l Da ta of 4: MS (EI) m/z (%) 724
(M+ - Fe - 7 CO, 2), 696 (M+ - Fe - 8 CO, 2), 668 (M+ - Fe
- 9CO, 2), 640 (M+ - Fe - 10 CO, 19), 584 (M+ - 2 Fe - 10
CO, 4), 558 (C32H34N2Fe2+, 13), 530 (C28H30N2Fe2+, 4), 515
(C29H27N2Fe2+, 15), 488 (C17H18NFe2(CO)5+, 14), 460 (C17H18
-
NFe2(CO)4+, 30), 432 (C17H18NFe2(CO)3+, 35), 404 (C17H18NFe2-
(CO)2+, 74), 376 (C17H18NFe2(CO)+, 2), 348 (C17H18NFe2+, 3),
265 (C11H7NFe2+, 4), 237 (C17H19N+, 39), 201 (C11H7N2Fe+, 5),
196 (C14H14N+, 23), 182 (C13H12N+, 15), 168 (C12H10N+, 31),
154 (C11H8N+, 49), 140 (C10H6N+, 18), 128 (C9H6N+, 29), 112
(Fe2+, 29), 84 (C6H12+, 100), 56 (Fe+, 94), 43 (C3H7+, 15); IR
(CH2Cl2, 298 K) [cm-1]: 2058 (m), 2047 (vs), 1985 (vs, br), 1770
(m); 1H NMR (CDCl3, 298 K) [ppm] 0.98-1.82 (m, 20H, CH2),
3.12-3.35 (m, 2H, CH), 6.72-7.95 (m, 14H, CH); 13C NMR
MS a n d Sp ectr oscop ica l Da ta of 7: MS (EI) m/z (%) 517
(M+, 2), 489 (M+ - CO, 5), 461 (M+ - 2 CO, 8), 433 (M+ - 4
CO, 7), 377 (M+ - 5 CO, 8), 349 (M+ - 6 CO, 14), 321 (M+
-
5CO - Fe, 13), 265 (C15H15NFe+, 18), 237 (C17H15N+, 76), 208
(C15H14N+, 48), 194 (C14H12N+, 69), 180 (C13H10N+, 33), 166
(C12H8N+, 30), 154 (C11H8N+, 78), 141 (C10H7N+, 86), 128
(C9H6N+, 63), 112 (Fe2+, 51), 84 (C6H12+, 100), 56 (Fe+, 86), 41
(C3H5+, 22); IR (CH2Cl2, 298 K) [cm-1] 2061 (m), 2048 (s), 2020
1
(vs), 1991 (sh), 1977 (vs, br); H NMR (CDCl3, 298 K) [ppm]

Reactivity of Naphthylimines toward Fe2(CO)9
Organometallics, Vol. 18, No. 23, 1999 4855
1.12-2.08 (m, 10H), 3.07 (d, 2J HH ) 21.3 Hz, 1H, part of a AB-
pattern of the diastereotopic protons at C9), 3.10-3.25 (m, 1H,
55), 199 (C10H9NFe+, 42), 171 (C8H5NFe+, 36), 141 (C10H9N+,
22), 112 (Fe2+, 27), 84 (C5H10N+, 45), 56 (Fe+, 56), 43 (C3H7
,
+
2
CH), 3.42 (d, J HH ) 21.3 Hz, 1H, part of a AB-pattern of the
11); IR (CH2Cl2, 298 K) [cm-1] 2064 (m), 2050 (s), 2023 (vs),
1
3
diastereotopic protons at C9), 5.90 (s, 1H, CH), 6.90-7.27 (m,
4H, CH), 8.17 (s, 1H, NdCH); 13C NMR (CDCl3, 298 K) [ppm]
25.4 (CH2), 25.7 (CH2), 25.8 (CH2), 31.8 (CH2), 34.0 (CH2), 34.7
(CH2), 70.0 (CH), 81.6 (C), 88.0 (C), 125.0 (CH), 126.0 (CH),
126.6 (CH), 128.6 (CH), 130.4 (CH), 141.3 (C), 179.0 (NdCH),
194.9 (CO). Anal. Calcd for C23H19NO6Fe2: C, 53.42; H, 3.70;
N, 2.71. Found: C, 52.26; H, 3.96; N, 2.85.
1984 (vs, br); H NMR (CDCl3, 253 K) [ppm] 3.55 (d, J HH )
6.3 Hz, 1H, CH), 3.63 (d, 3J HH ) 6.0 Hz, 1H, CH), 3.98 (d, 2J HH
) 12.1 Hz, 1H, part of a AB-pattern of the diastereotopic
protons at C11), 4.08 (d, J HH ) 12.1 Hz, 1H, part of a AB-
2
pattern of the diastereotopic protons at C11), 6.32-6.36 (m,
2H, CH), 6.69 (s, 1H, CH), 6.96-7.54 (m, 6H, CH); 13C NMR
(CDCl3, 253 K) [ppm] 61.9 (CH), 62.0 (CH), 76.4 (CH2), 86.7
(CH), 86.9 (CH), 118.5 (CH), 119.9 (C), 123.8 (CH), 128.6 (C),
128.8 (CH), 129.4 (CH), 139.3 (CH), 143.8 (C), 145.7 (C), 158.7
MS a n d Sp ectr oscop ica l Da ta of 8: MS (EI) m/z (%) 657
(M+, 1), 629 (M+ - CO, 16), 601 (M+ - 2 CO, 1), 573 (M+ - 3
CO, 31), 545 (M+ - 4 CO, 36), 517 (M+ - 5 CO, M+ - 3 CO -
Fe, 43), 489 (M+ - 6 CO, M+ - 4 CO - Fe, 100), 451 (M+ - 7
CO, M+ - 5 CO - Fe, 72), 433 (M+ - 8 CO, M+ - 6 CO - Fe,
73), 405 (M+ - 9 CO, M+ - 7 CO - Fe, 100), 377 (M+ - 8 CO
- Fe, M+ - 6 CO - Fe, 58), 349 (M+ - 9 CO - Fe, M+ - 7 CO
- Fe, 84), 321 (M+ - 8 CO - 2 Fe, 293), 293 (M+ - 8 CO - 2
Fe, 30), 265 (M+ - 9 CO - 3 Fe, 51), 201 (C14H19N+, 91), 196
(C), 208.4 (CO), 210.3 (CO), 210.6 (CO). Anal. Calcd for C26H13
-
NO9Fe3: C, 47.98; H, 2.01; N, 2.15. Found: C, 48.12; H, 2.09;
N, 2.25.
MS a n d Sp ectr oscop ica l Da ta of 10: MS (EI) m/z (%)
371 (M+, 2), 343 (M+ - CO, 8), 315 (M+ - 2 CO, 20), 287 (M+
- 3 CO, 82), 230 (C17H12N+, 100), 202 (C15H8N+, 11), 144
(C10H10N+, 15), 115 (C8H5N+, 12), 77 (C6H5+, 24), 56 (Fe+, 19);
IR (CH2Cl2, 298 K) [cm-1] 2064 (vs), 2021 (vs), 1989 (vs, br),
1967 (sh); 1H NMR (CDCl3, 253 K) [ppm] 5.29 (s, 1H, CH),
(C14H14N+, 49), 182 (C13H12N+, 49), 167 (C12H9N+, 38), 154
(C11H8N+, 28), 141 (C10H7N+, 47), 112 (Fe2+, 38), 84 (C6H12
,
+
78), 56 Fe+, 39); IR (CH2Cl2, 298 K) [ppm] 2060 (m), 2048 (s),
2019 (s), 1976 (vs, br); H NMR (CDCl3, 298 K) [ppm] 0.95-
3
3
6.50 (d, J HH ) 7.7 Hz, 1H, CH), 6.61 (d, J HH ) 7.7 Hz, 1H,
CH), 6.7-7.8 (m, 10H, CH); 13C NMR (CDCl3, 253 K) [ppm]
53.6 (CH), 89.6 (C), 113.6 (CH), 120.5 (CH), 121.1 (CH), 124.9
(CH), 126.1 (CH), 126.2 (CH), 127.4 (CH), 127.7 (CH), 128.1
(CH), 128.9 (CH), 129.1 (CH), 129.3 (CH), 136.9 (C), 137.6 (C),
146.6 (C), 208.2 (CO), 209.1 (CO). Anal. Calcd for C20H13NO3-
Fe: C, 64.72; H, 3.53; N, 3.77. Found: C, 64.23; H, 3.61; N,
3.58.
1
3
1.90 (m, 10H, CH2), 2.05-2.28 (m, 1H, CH), 3.50 (dd, J HH
)
4
2
5.8 Hz, J HH ) 1.9 Hz, 1H, CH), 3.51 (d, J HH ) 11.8 Hz, 1H,
part of a AB-pattern of the diastereotopic protons at C11), 3.62
3
4
2
(dd, J HH ) 5.8 Hz, J HH ) 1.9 Hz, 1H, CH), 3.75 (d, J HH
)
11.8 Hz, 1H, part of a AB-pattern of the diastereotopic protons
at C11), 6.26-6.37 (m, 2H, CH), 6.58 (s, 1H, CH), 7.21 (s, 1H,
CH); 13C NMR (CDCl3, 298 K) [ppm] 25.9 (CH2), 26.0 (CH2),
26.3 (CH2), 35.1 (CH2), 35.8 (CH2), 62.1 (CH), 62.4 (CH), 64.7
(CH), 74.0 (CH2), 86.6 (CH), 86.9 (CH), 117.6 (CH), 124.9 (C),
138.8 (C), 140.0 (CH), 140.6 (C), 146.5 (C), 208.3 (CO), 210.7
(CO), 211.0 (CO). Anal. Calcd for C26H19NO9Fe3 C, 47.53; H,
2.91; N, 2.13. Found: C, 47.72; H, 3.03; N, 1.98.
Ack n ow led gm en t. The author gratefully thanks
the Deutsche Forschungsgemeinschaft (SFB 436) for
financial support.
MS a n d Sp ectr oscop ica l Da ta of 9: MS (EI) m/z (%) 651
(M+, 1), 623 M+ - CO, 3), 595 (M+ - 2 CO, 2), 567 (M+ - 3
CO, 10), 539 (M+ - 4 CO, 6), 511 (M+ - 5 CO, M+ - 3 CO -
Fe, 8), 483 (M+ - 6 CO, M+ - 4 CO - Fe, 40), 455 (M+ - 7
CO, M+ - 5 CO - Fe, 37), 427 (M+ - 8 CO, M+ - 6 CO - Fe,
27), 399 (M+ - 9 CO, M+ - 7 CO - Fe, 44), 371 (M+ - 8 CO
- Fe, M+ - 6 CO - 2 Fe, 25), 343 (M+ - 9 CO - Fe, M+ - 7
CO - 2 Fe, 87), 287 (M+ - 9 CO - 2 Fe, 100), 230 (C17H12N+,
Su p p or tin g In for m a tion Ava ila ble: Details about the
X-ray crystal structures including ORTEP diagrams of the
crystal packings, tables of crystal data and structure refine-
ment, atomic coordinates, bond lengths and angles, and
anisotropic displacement parameters for 1-10. This material
is available free of charge via the Internet at http://pubs.acs.org.
OM990067Z