Reaction chemistry of tricarbonyl-η5-pentadienylmanganese: Straightforward synthesis of stable manganese carbonyl terminal thiolates and a dinuclear bis(ethylenediaminyl) complex

Article abstract of DOI:10.1016/j.jorganchem.2010.08.005

Tricarbonyl-η⁵-pentadienylmanganese reacts with mercaptans RSH, R = Ph, C₆F₅, m-NH₂C₆H ₄, p-NH₂C₆H₄, and HSCH ₂CH₂ in the presence of ECH₂CH₂E, E = -PPh₂ or -NH₂ to give novel stable terminal thiolate mononuclear complexes fac-Mn(CO)₃(SR)(Ph₂PCH ₂CH₂PPh₂-κ²-P,P′) for R = Ph, C₆F₅, m-NH₂C₆H₄, p-NH₂C₆H₄, and HSCH₂CH₂ and fac-Mn(CO)₃(SR)(H₂NCH₂CH₂NH ₂-κ²-N,N′) for R = Ph and C₆F ₅. Upon reaction of tricarbonyl-η⁵- pentadienylmanganese with ethylenediamine a dinuclear complex [fac-Mn(CO) ₃(μ-H₂NCH₂CH₂NH- κ²-N,N′)]₂ was formed wherein the diaminyl ligand functions in the capacity of chelating and bridging ligand.

Full text of DOI:10.1016/j.jorganchem.2010.08.005

Journal of Organometallic Chemistry 695 (2010) 2548e2556
Contents lists available at ScienceDirect
Journal of Organometallic Chemistry
journal homepage: www.elsevier.com/locate/jorganchem
Reaction chemistry of tricarbonyl-
h
5-pentadienylmanganese: Straightforward
synthesis of stable manganese carbonyl terminal thiolates and a dinuclear bis
(ethylenediaminyl) complex
*
Karla Patricia Salas-Martin, Marisol Reyes-Lezama, Noé Zúñiga-Villarreal
Instituto de Química, Universidad Nacional Autónoma de México, Ciudad Universitaria, Circuito Exterior, 04510 México, D.F., México
a r t i c l e i n f o
a b s t r a c t
Article history:
Tricarbonyl-
h
5-pentadienylmanganese reacts with mercaptans RSH, R ¼ Ph, C6F5, m-NH2C6H4,
Received 18 June 2010
Received in revised form
4 August 2010
Accepted 4 August 2010
Available online 13 August 2010
p-NH2C6H4, and HSCH2CH2 in the presence of ECH2CH2E, E ¼ ePPh2 or eNH2 to give novel stable
terminal thiolate mononuclear complexes fac-Mn(CO)3(SR)(Ph2PCH2CH2PPh2-k2-P,P0) for R ¼ Ph, C6F5, m-
NH2C6H4, p-NH2C6H4, and HSCH2CH2 and fac-Mn(CO)3(SR)(H2NCH2CH2NH2-k2-N,N0) for R ¼ Ph and C6F5.
Upon reaction of tricarbonyl-
Mn(CO)3(
of chelating and bridging ligand.
h
5-pentadienylmanganese with ethylenediamine a dinuclear complex [fac-
m
-H2NCH2CH2NH-k2-N,N0)]2 was formed wherein the diaminyl ligand functions in the capacity
Keywords:
Ó 2010 Elsevier B.V. All rights reserved.
Ethylendiaminyl complexes
Manganese carbonyl thiolates
Pentadienyl ligand
1,2-Bis(diphenylphosphino)ethane
Nucleophilic attack on pentadienyls
1. Introduction
one bridging carbonyl were obtained upon reaction of Mn(h
5-C5H7)
(CO)3 with mercaptans in the presence of tertiary phosphines
(Scheme 1b) [3b]. Selenium analogs of the above mentioned sulfur
complexes were prepared by one pot syntheses; in addition,
a selenium heterocubane and a terminal phenylselenolate complex
could be obtained (Scheme 1a and c) [3c].
Transition metal pentadienyl complexes have been thoroughly
studied [1]. As far as their reaction chemistry is concerned
nucleophilic attack on pentadienyl complexes has been exten-
sively explored [2]. Several years ago we reported on the reaction
chemistry of tricarbonyl-
h
5-pentadienylmanganese towards
Terminal thiolates of mononuclear manganese carbonyls are
often unstable to CO loss to form thiolate-bridged dinuclear
species [5]. Stabilization of mononuclear terminal thiolate
carbonyls can be accomplished either by introducing electron-
withdrawing substituents in the mercaptan backbone in order to
lower the basicity of the sulfhydryl sulfur atom or by coordi-
nation of electron rich ligands to the metal center to prevent CO
substitution. As an example of the first case it was possible to
isolate and characterize the mononuclear pentacarbonyl complex
Mn(CO)5SC6F5 [6]. To date and to the best of our knowledge no
examples of the second case have been reported; this can be
ascribed to the synthetic difficulty posed by the introduction of
a thiolate ligand to an electron rich metal center. With a view of
extending the application of the pentadienyl-extrusion synthetic
approach and encouraged by the realization of a terminal sele-
nolate complex we set out to explore the influence of 1,2-bis
(diphenylphosphino)ethane (dppe) and ethylenediamine on the
mercaptans [2d,3a]. We found that in the resulting products the
pentadienyl ligand was not present (Scheme 1a). Such ligand loss
is not uncommon in the chemistry of polyenyl metal carbonyls
[4]; however, one remarkable aspect of this process is that the
vacant sites available after enyl elimination can be potentially
occupied by virtually any ligand present in the reaction medium
provided that the polyenyl adds a hydrogen atom to form the
corresponding polyene in order to leave the metal center coor-
dination sphere.
In the light of such assumptions we decided to undertake
a study of the synthetic possibilities that the pentadienyl ligand
offers when extruded from the metal’s coordination sphere. We
have found that binuclear complexes with two thiolate bridges and
* Corresponding author. Tel.: þ52 5622 44 31; fax: þ52 56 16 22 03.
E-mail address: zuniga@unam.mx (N. Zúñiga-Villarreal).
reaction of mercaptans with Mn(h
5-C5H7)(CO)3.
0022-328X/$ e see front matter Ó 2010 Elsevier B.V. All rights reserved.
doi:10.1016/j.jorganchem.2010.08.005

K.P. Salas-Martin et al. / Journal of Organometallic Chemistry 695 (2010) 2548e2556
2549
Scheme 1.
2. Results and discussion
dppe the reaction gave a mixture of heterocubane [Mn(m3-SPh)
(CO)3]4 [3a] and (2). Addition of 1,2-ethanedithiol to a solution of
2.1. Complexes fac-Mn(CO)3(SR)(Ph2PCH2CH2PPh2-k2-P,P0), R ¼ Ph,
(2), C6F5, (3) m-NH2C6H4 (4), p-NH2C6H4, (5); HSCH2CH2, (6)
Mn(h
5-C5H7)(CO)3 without dppe in the reaction medium afforded
a trinuclear complex [7] instead of complex (6). Addition order
for preparing (3)e(5) posed no problems; since, neither C6F5SH,
Reaction of pentadienyl complex (1) with mercaptans RSH,
R ¼ Ph, C6F5, m-NH2C6H4, p-NH2C6H4, and HSCH2CH2 in the pres-
ence of dppe afforded complexes (2)e(6) as shown in Scheme 2.
The reactions were conducted under cyclohexane reflux with
equimolar ratios of (1) and the corresponding mercaptan. Reaction
times were from 1 to 2 h (see experimental for further details).
Yields fell within the range 85.0e96.0%. Complexes (2) and (3) are
light yellow solids whereas (4)e(6) are greenish-brown solids; all
complexes were stable for several weeks in the solid state in air and
in solution they stood from 1 to 2 days without decomposing
(at low temperature they can be stored under nitrogen for an
indefinite period).
m-NH2C6H4SH nor p-NH2C6H4SH reacts with Mn(h
5-C5H7)(CO)3
at cyclohexane boiling temperature. Due to low solubility of
(4) and (5) in cyclohexane their reaction times were determined
by monitoring the disappearance of the IR
C5H7)(CO)3; for all other complexes the reaction times were
established by monitoring the final products’ IR (CO) bands.
n -
(CO) bands of Mn(h5
n
Complexes (2)e(6) are octahedral and possess a Cs point group
that gives rise to three carbonyl stretching modes (2A0 þ A00) in their
IR spectra [8]. It can be concluded from IR data of complexes (2)e(6)
(see Experimental) that there is no distinct general correlation
between the electronic or steric properties of the thiolates and their
n
(CO) bands.
Addition order of reagents was instrumental in the formation
of (2) and (6); since, when phenyl mercaptan was added before
Formation of mononuclear dppe complexes can be divided into
two categories depending on the relative dppe’s nucleophilicity
against the mercaptans’. The first category takes in the formation of
complexes (2) and (6) since phenyl mercaptan and 1,2-ethanedi-
thiol are stronger nucleophiles than dppe towards [Mn(
(CO)3]: (i) initial coordination of the mercaptan to the metal center
h
5-C5H7)
of Mn(
(Scheme 3).
This reaction step would involve an
h
5-C5H7)(CO)3 would generate an h3 intermediate
A
h
3-species. These species
are well known as intermediates in carbonyl substitution reactions
of (1) by tertiary phosphines and phosphites [9]. (ii) Hydrogen
migration from the sulfur atom of the coordinated mercaptan to the
h
3-pentadienyl ligand of A would afford intermediate B. It is
apparent from IR and 1H-NMR monitoring of the reactions that
mercaptan coordination as well as intramolecular hydrogen
migration are relative fast processes that preclude detection of
intermediates A and B. The formation of cis-pyperilene detected by
Scheme 2.

2550
K.P. Salas-Martin et al. / Journal of Organometallic Chemistry 695 (2010) 2548e2556
Scheme 3.
1H-NMR in the reaction medium as in the closely related process
where phenyl mercaptan attacks Mn(
5-C5H7)(CO)3 to give dinu-
clear carbonyl complexes [3b] suggests the presence of B. (iii)
Substitution of cis-pyperilene by dppe gives mononuclear
an S-
conformation has been reported for the
the complex Mn(
3-C5H7)(CO)3(PMe3) [9]. Coordination by the
other dppe phosphorus atom with concomitant elimination of
trans-pyperilene afford the final product.
Mononuclear manganese carbonyl complexes with chelating
dppe have been extensively reported [12]; however, terminal
manganese carbonyl thiolates with dppe are scarce [13].
The structures obtained by single crystal X-ray diffraction of
(2)e(5) are shown from Figs. 1e4. In all cases the complexes’
structures are similar and exhibit a distorted octahedral geometry
around the manganese atom with a fac arrangement of the carbonyl
groups. The MneS distances are all comparable within experi-
mental error. The geometry around the sulfur atom is angular with
two lone pairs (sp3 hybridization).
h
3-pentadienyl ligand (see Scheme 4, intermediate C). This
3-pentadienyl ligand in
h
h
h
a
complex with a terminal thiolate. It is known that conjugate diene
carbonemetal bonds to transition metals are more stable than
isolated olefins [10]; notwithstanding, in the present case step (iii)
cis-pyperilene yields its coordination sites to dppe which stabilizes
the terminal thiolate complex. Thus, dppe chelation is preferred
over diene chelation. We propose step (iii) for the transformation of
B to the final product; although, we are aware that several steps
could be involved. The second category covers the mercaptans that
are less nucleophilic than dppe. Mercaptans C6F5SH, m-NH2C6H4SH,
and p-NH2C6H4SH do not react towards Mn(h
5-C5H7)(CO)3 in
boiling cyclohexane; so, formation of complexes (3), (4), and (5)
must take place by initial attack by dppe. We propose in this case
the mechanism shown in Scheme 4.
Step (i) consists in the formation of
h
3-complex C by dppe
2.2. Complexes fac-Mn(CO)3(SR)(H2NCH2CH2NH2-k2-N,N0), R ¼ Ph
(7) and C6F5 (8)
monocoordination. We tried to obtain this intermediate by reaction
of (1) with dppe according to Eq. (1). The reaction resulted in
a mixture of products that could not be characterized [11].
Reaction of pentadienyl complex (1) with mercaptans RSH,
R ¼ Ph and C6F5, in the presence of ethylenediamine gave (7) and
(8) as shown in Scheme 5.
Monitoring of the reaction by 1H-NMR for preparation of (3)
in an NMR tube showed the occurrence of trans-pyperilene in
60 min at 45 ꢀC. This suggests that hydrogen migration occurs to
Fig. 1. Molecular structure of (2) including the atom numbering scheme (ORTEP
drawing with 50% probability ellipsoids). Only phenyl ipso carbon atoms are shown for
ꢀ
ꢀ
clarity. Selected bond lengths [A] and angles [ ]: Mn(1)eC(1) 1.799(4); Mn(1)eC(3)
1.774(4); Mn(1)eS(1) 2.411(1); Mn(1)eP(1) 2.326(1). S(1)eMn(1)eC(3) 178.4(1), C(1)e
Mn(1)eP(1) 169.8(1), C(2)eMn(1)eP(2) 174.7(1), C(4)eS(1)eMn(1) 110.9(1), P(1)eMn
(1)eP(2) 84.41(4).
Scheme 4.

K.P. Salas-Martin et al. / Journal of Organometallic Chemistry 695 (2010) 2548e2556
2551
Fig. 2. Molecular structure of (3) including the atom numbering scheme (ORTEP
drawing with 50% probability ellipsoids). Only phenyl ipso carbon atoms are shown for
clarity. Partial occupancy of crystallization solvent is not shown. Selected bond lengths
[A] and angles [ ]: Mn(1)eC(7) 1.797(3); Mn(1)eC(8) 1.834(3); Mn(1)eS(1) 2.4154(7);
Mn(1)eP(1) 2.3095(7). S(1)eMn(1)eC(7) 173.90(8), C(9)eMn(1)eP(1) 178.55(8), C(8)e
Mn(1)eP(2) 174.18(8), C(1)eS(1)eMn(1) 113.02(9), P(1)eMn(1)eP(2) 85.02(2).
Fig. 4. Molecular structure of (5) including the atom numbering scheme (ORTEP
drawing with 50% probability ellipsoids). Only phenyl ipso carbon atoms are shown for
clarity. Selected bond lengths [A] and angles [ ]: Mn(1)eC(1) 1.813(3); Mn(1)eC(2)
1.790(3); Mn(1)eS(1) 2.4098(9); Mn(1)eP(1) 2.3194(8). S(1)eMn(1)eC(2) 177.97(10),
C(1)eMn(1)eP(1) 174.10(9), C(3)eMn(1)eP(2) 169.59(10), C(6)eS(1)eMn(1) 110.93(9),
P(1)eMn(1)eP(2) 84.52(3).
ꢀ
ꢀ
ꢀ
ꢀ
The reactions were carried out under cyclohexane reflux with
equimolar ratio; the reaction yields were around 70% for both
complexes. Complexes (7) and (8) are light yellow solids insoluble
in hydrocarbons; (7) is partially soluble in alkyl chlorides, while (8)
is soluble. Both complexes were stable for several weeks in the solid
state in air; in solution they decomposed within two weeks (at low
temperature they can be stored under nitrogen for an indefinite
period).
The infrared spectra of (7) and (8) present n(CO) bands (2015,
1919, 1897 and 2022, 1926, 1906 cmꢁ1 all strong, in CH2Cl2 for (7)
and (8) resp.) with similar shape and wave numbers to those of
(2)e(6) (see Table 1); notwithstanding, one perceptible difference
is observed in the wave number of the band assigned to the A00
stretching mode (1919 and 1926 cmꢁ1, for (7) and (8), resp.). It has
been proposed that this band stems from the out-of-phase vibra-
tion (antisymmetric with respect to the mirror plane of the mole-
cule) of equatorial carbonyls [8] that in (7) and (8) are trans to the
ethylenediamine eNH2 groups. This fact suggests that ethylenedi-
amine donates more electron density to the manganese than it can
receive, if at all, rendering the A00 mode
n(CO) band to appear at
lower wave number than in (2)e(6).
The relative nucleophilicities of ethylenediamine vs. PhSH and
C6F5SH are apparent from the reaction times. It has already been
pointed out that C6F5SH does not react with (1) at cyclohexane
reflux temperature. So, formation of (7) takes place in 2 h by
Fig. 3. Molecular structure of (4) including the atom numbering scheme (ORTEP
drawing with 50% probability ellipsoids). Only phenyl ipso carbon atoms are shown for
clarity. Partial occupancy of crystallization solvent is not shown. Selected bond lengths
ꢀ
ꢀ
[A] and angles [ ]: Mn(1)eC(1) 1.786(4); Mn(1)eC(2) 1.805(4); Mn(1)eS(1) 2.406(1);
Mn(1)eP(1) 2.334(1). S(1)eMn(1)eC(1) 175.34(12), C(3)eMn(1)eP(1) 176.24(12),
C(2)eMn(1)eP(2) 169.19(13), C(6)eS(1)eMn(1) 115.5(1), P(1)eMn(1)eP(2) 84.02(3).
Scheme 5.

2552
K.P. Salas-Martin et al. / Journal of Organometallic Chemistry 695 (2010) 2548e2556
Table 1
Crystal data for (2)e(5), (7)e(9).
(2)
(3)
(4)
(5)
Empirical formula
M
C35H29MnO3P2S
646.52
C35H24F5MnO3P2S with toluene
828.62
C35H30MnNO3P2S with ½ of CH2Cl2
704.00
C35H30MnNO3P2S
661.54
Temperature (K)
Crystal size (mm)
Crystal system
Space group
293(2)
100(2)
298(2)
298(2)
0.24 ꢂ 0.22 ꢂ 0.12
Monoclinic
P21/c
11.846(1)
18.253(1)
14.498(1)
90
96.992(1)
90
0.42 ꢂ 0.34 ꢂ 0.29
0.30 ꢂ 0.22 ꢂ 0.18
Monoclinic
P21/c
0.38 ꢂ 0.32 ꢂ 0.30
Monoclinic
P21/c
11.9575(9)
17.7232(13)
15.0621(11)
90
96.264(2)
90
3173.0(4)
Triclinic
P
ꢁ1
ꢀ
a (A)
11.1234(7)
13.0909(8)
14.3952(9)
90
108.5560(10)
95.2980(10)
1880.1(2)
8.8228(4)
ꢀ
b (A)
33.2242(15)
11.9256(5)
90
108.1140(10)
90
ꢀ
c (A)
a
b
g
(ꢀ)
(ꢀ)
(ꢀ)
3
ꢀ
V (A )
3111.3(3)
3322.5(3)
Z
q
4
2
4
4
Range for data collection (ꢀ)
1.73e25.02
25,279
1.57e25.00
10,695
1.23e25.00
27,208
1.71e25.00
25,530
Reflections collected
Independent reflections
5484 (Rint ¼ 0.0635)
R1 ¼ 0.0540, wR2 ¼ 0.0696
R1 ¼ 0.0884, wR2 ¼ 0.0735
6558 (Rint ¼ 0.0211)
R1 ¼ 0.0403, wR2 ¼ 0.1020
R1 ¼ 0.0442, wR2 ¼ 0.1048
5853 (Rint ¼ 0.0638)
R1 ¼ 0.0594, wR2 ¼ 0.1137
R1 ¼ 0.0780, wR2 ¼ 0.1214
5577 (Rint ¼ 0.0388)
R1 ¼ 0.0453, wR2 ¼ 0.1072
R1 ¼ 0.0608, wR2 ¼ 0.1127
Final R indices [F2 > 2
s
(F2)]
R indices (all data)
(7)
(8)
(9)
Empirical formula
M
C
11H13MnN2O3S
C11H8F5MnN2O3S
398.19
298(2)
0.28 ꢂ 0.24 ꢂ 0.06
Monoclinic
P21/c
C10H14Mn2N4O6
396.13
298(2)
308.23
298(2)
Temperature (K)
Crystal size (mm)
Crystal system
Space group
0.40 ꢂ 0.28 ꢂ 0.24
0.33 ꢂ 0.14 ꢂ 0.08
Orthorhombic
Triclinic
Pbca
14.5032(10
10.6241(7)
17.4978(12)
90
90
90
2696.1(3)
P
ꢁ1
6.7643(10)
8.0924(11)
8.1427(12)
62.566(2)
88.754(2)
70.872(2)
369.29(9)
ꢀ
a (A)
10.1409(8
ꢀ
b (A)
14.7688(12)
10.2144(8)
90
108.9600(10)
90
ꢀ
c (A)
a
b
g
(ꢀ)
(ꢀ)
(ꢀ)
3
ꢀ
V (A )
1446.8(2)
Z
q
8
4
1
Range for data collection (ꢀ)
2.33e25.00
20,245
2.46e25.37
11,823
2.85e25.00
2973
Reflections collected
Independent reflections
2379 (Rint ¼ 0.0421)
R1 ¼ 0.0308, wR2 ¼ 0.0674
R1 ¼ 0.0394, wR2 ¼ 0.0700
2656 (Rint ¼ 0.0381)
R1 ¼ 0.0330, wR2 ¼ 0.0712
R1 ¼ 0.0422, wR2 ¼ 0.0739
1299 (Rint ¼ 0.0309)
R1 ¼ 0.0304, wR2 ¼ 0.0720
R1 ¼ 0.0339, wR2 ¼ 0.0733
Final R indices [F2 > 2
s
(F2)]
R indices (all data)
initial attack of PhSH, whereas initial attack by ethylenediamine
leads to complex (8) in 13 h. Both complexes possess free eNH2
groups. This speaks of the stability of the pentadienyl ligand to
NeH addition of ethylenediamine; since, it is known that primary
and secondary amines react with (1), at cyclohexane reflux
temperature, with NeH bond scission and NeC(pentadienyl)
bond formation to afford aminopentenyl complexes [2f]. The
reciprocal effect between the eNH2 groups and the presence of
C6F5SH in the present case prevent ethylenediamine attack to (1)
in any other way than coordination through the diamine lone
pairs: ethylenediamine in (7) and (8) is ligated in a chelate
fashion.
As in the case of (2)e(6) two mechanisms of formation can be
envisioned for achieving (7) and (8). The first would be analogous
to the one shown in Scheme 3, where phenyl mercaptan attacks (1)
to give an
h
3-species. The second proposed mechanism would
resemble that in Scheme 4 with ethylenediamine initially attacking
complex (1).
A large number of manganese carbonyl complexes exist that
contain MneN bonds; in most of them the nitrogen atom is that of
an imine, imide or part of an aromatic system [14], however,
primary diamine chelators with carbonyl manganese thiolates are
virtually unknown [13]. Complexes (7)e(9) leave open the possi-
bility for further reaction chemistry at the NH2 groups.
The X-ray structures of (7) and (8) are shown in Figs. 5 and 6,
respectively.
Fig. 5. Molecular structure of (7) including the atom numbering scheme (ORTꢀEP
ꢀ
drawing with 50% probability ellipsoids). Selected bond lengths [A] and angles [ ]:
MneC(1) 1.786(2); MneC(3) 1.800(3); MneS 2.3916(6); MneN(1) 2.083(2). SeMneC
(3) 174.73(8), C(1)eMneN(1) 174.62(9), C(2)eMneN(2) 173.57(9), C(6)eSeMn 117.69
(7), N(1)eMneN(2) 80.19(8).

K.P. Salas-Martin et al. / Journal of Organometallic Chemistry 695 (2010) 2548e2556
2553
Fig. 7. Molecular structure of (9) including the atom numbering scheme (ORTꢀEP
Fig. 6. Molecular structure of (8) including the atom numbering scheme (ORTEP
ꢀ
ꢀ
ꢀ
drawing with 50% probability ellipsoids). Selected bond lengths [A] and angles [ ]:
drawing with 50% probability ellipsoids). Selected bond lengths [A] and angles [ ]: Mn
(1)eC(1) 1.795(3); Mn(1)eC(2) 1.803(3); Mn(1)eS(1) 2.4212(7); Mn(1)eN(1) 2.096(2).
S(1)eMn(1)eC(1) 178.05(8), C(3)eMn(1)eN(1) 175.04(10), C(2)eMn(1)eN(2) 172.27
(10), C(6)eS(1)eMn(1) 109.70(8), N(1)eMn(1)eN(2) 80.46(8).
MneC(1) 1.803(3); MneC(3) 1.790(3); MneN(1) 2.049(2); MneN(2) 2.089(2). C(1)e
MneN(1) 170.10(10), C(2)eMneN(1A) 175.37(9), C(3)eMneN(2) 174.18(11), MneN
(1)eMn(1) 100.97(8).
pentadienyl ligand may take place. In the absence of any suitable
hydrogen atom (like that of a mercaptan’s sulfhydryl group)
ethylenediamine NH hydrogens saturate the pentadienyl ligand to
trans-pyperilene; so, ethylenediamine in (9) acts as chelating and
bridging ligand to realize an 18 electron configuration at each
manganese center. The structure of (9), determined by an X-ray
analysis, is shown in Fig. 7.
Both present an octahedral geometry around the metal center
with the carbonyls in a fac disposition. In comparison with the
structures of (2)e(5) the distortion from an octahedral geometry in
(7) and (8) is slightly greater due to the smaller size of the nitrogen
atom compared with the phosphorus atom; this is reflected in the
NeMneN angles (around 80ꢀ) vs. PeMneP angles (ca 84ꢀ). The
MneS distances in all mononuclear complexes here reported fall in
the range 2.3916(6)ꢀe2.4212(7)ꢀ. The manganeseecarbon atom
distances of the carbonyl groups are all similar within each
complex: no trans effect is noticeable whatsoever.
Both manganese atoms present a distorted octahedral geometry
due to the amineeamide bridges. There are two MneN distances:
for MneNH and MneNH2 bonds being the former shorter (2.049
ꢀ
(2), 2.089(2) A, resp.). The geometry around nitrogen atoms speaks
of an sp3 hybridization. The MneCO bond distances are all equal
2.3. Complex [fac-Mn(CO)3(m
-H2NCH2CH2NH-k2-N,N0)]2, (9)
within experimental error.
Reaction of (1) with ethylenediamine (molar ratio 8:1,
amine:(1)) at cyclohexane reflux temperature for 12 h afforded
complex (9) as a yellow solid with low yield (21%) according to
Eq. (2).
3. Conclusions
Terminal new carbonyl manganese thiolates could easily be
obtained by means of
a straightforward reaction involving
bifunctional phosphorus and nitrogen ligands. In both cases the
ligands acted as chelators; forcing reaction conditions rendered
ethylenediamine reactive towards tricarbonyl(h
5-pentadienyl)
manganese to achieve a dinuclear complex with two ethyl-
enediaminyl moieties bridging two Mn(CO)3 fragments via two
(
m
ꢁNH) interactions while the other two eNH2 groups bind each
a metal center through their lone electron pairs. Bridging and/or
chelating capacities of ethylenediamine towards manganese
depend on the presence of hydrogen atoms attached to
nitrogen: Chelation is achieved when NH2 groups remain intact;
while NeH scission led to obtaining bridging ethylenediaminyl.
(9) is insoluble in hydrocarbons but readily dissolves in chlori-
nated hydrocarbons. The stability of (9) is remarkable: after one
month in air it did not decompose. Unreacted (1) could be recov-
ered by extraction with hexane from the reaction mixture. The IR
Our studies have shown that tricarbonyl-h
5-pentadienylmanga-
spectrum of (9) shows five
n
(CO) bands for terminal carbonyls.
nese is an adequate starting material to prepare diverse
manganese carbonyls with ligands of the group 15 and 16
bonded to the same coordination sphere. We anticipate that the
synthetic method here reported has great potential; further
work is underway.
Diamine concentration (8:1 molar ratio) and reaction time
(12 h) point out the difficulty for this process to occur and
suggest that ethylenediamine coordination to manganese is
necessary so that NeH bond cleavage and H migration to the

2554
K.P. Salas-Martin et al. / Journal of Organometallic Chemistry 695 (2010) 2548e2556
4. Experimental
Complex fac-Mn(CO)3(SC6F5)(Ph2PCH2CH2PPh2-k2-P,P0) (3). Pen-
tafluorophenyl mercaptan, 2.43 mmol, 485 mg; (1) 2.43 mmol,
500 mg; dppe 2.43 mmol, 967 mg. Reaction time: 1 h 40 min. Anal.
found (calcd.) (3)$toluene: C 61.3 (60.9); H 3.59 (3.89). Yield 92.0%.
General considerations. All reactions were conducted under
nitrogen atmosphere using standard vacuum line and Schlenk
techniques. The reactions were monitored by IR spectroscopy in the
M.p.146 ꢀCdec. IR(KBr): (CO)2012s,1946 s,1920s, cmꢁ1. IR(CHCl3):
n
n
(CO) region and the reaction times reported correspond to the
n d/ppm:
(CO) 2018 s,1952 s,1920 s, cmꢁ1.1H-NMR (CDCl3, 300 MHz):
time when no further changes were observed in the CO groups’
patterns. Complex (1) [15] was prepared according to literature
procedures. 1,2-Bis(diphenylphosphino)ethane, ethylenediamine,
7.22e7.78 [m, 20H, (H5C6)2P(CH2)2P(C6H5)2]; 3.13 [s, 2H,
(H5C6)2PCH2CH2P(C6H5)2]; 2.71 [s, 2H, (H5C6)2PCH2CH2P(C6H5)2].
31P-NMR{1H} (CDCl3, 121.7 MHz):
d
/ppm: 72.0 s. 19F-NMR{1H}
1,2-ethanedithiol,
phenyl
mercaptan,
pentafluorophenyl
(CDCl3, 282 MHz):
d
/ppm: ꢁ127.95 [d, Fo, eS(C6F5), JFoeFm ¼ 24.5 Hz],
mercaptan, m-, and p-aminothiophenols were acquired from
Aldrich Chemical Co. and used as received. IR spectra were obtained
in solution (4000e580 cmꢁ1) using a Nicolet FT-IR 55X spectrom-
eter and in KBr disk (4000e200 cmꢁ1) in a Perkin Elmer 283B
spectrometer. NMR spectra were obtained at room temperature on
Varian Unity 300, Perkin Elmer 283B, and Jeol GX300 spectrome-
ters. 1H-NMR spectra were referenced to residual solvent peaks
ꢁ161.93 [t, Fp, eS(C6F5), JFpeFm ¼ 20.88 Hz], ꢁ164.78 [t, Fm, eS(C6F5),
JFmeFo, Fp ¼ 22 Hz], 13C{1H}-NMR (CDCl3, 75.6 MHz):
d/ppm: 134.87
[t, Ci, Ph2P(CH2)2PPh2, JCieP ¼ 18.82 Hz]; 131.57 [d, Co, Ph2P
(CH2)2PPh2, JCoeP ¼ 24.33 Hz]; 130.28 [d, Cm, Ph2P(CH2)2PPh2,
JCmeP ¼ 21.00 Hz]; 128.61 [d, Cp, Ph2P(CH2)2PPh2, JCpeP ¼ 48.74 Hz];
24.62 [t, CCH , Ph2P(CH2)2PPh2, J
¼ 21:00 Hz]. FABþ MS (m/e):
CH2ꢁP
2
652 [M ꢁ 3CO]þ, 537 [M ꢁ S(C6F5)]þ, 453 [M ꢁ 3CO ꢁ S(C6F5)]þ.
Complex fac-Mn(CO)3(SC6H4-m-NH2)(Ph2PCH2CH2PPh2-k2-P,P0)
(4). m-Aminothiophenol 2.43 mmol, 304 mg; (1) 2.43 mmol, 500 mg;
dppe 2.43 mmol, 967 mg. Reaction time: 2 h. Anal. found (calcd.): C
with chemical shifts (d) reported in ppm downfield of tetrame-
thylsilane. 31P{1H} NMR spectra were externally referenced to 85%
H3PO4. FAB(þ) mass spectra were recorded on a JEOL SX-102A
instrument. Elemental analyses were performed by Galbraith
Laboratories, Inc. Knoxville, TN. USA. Melting points were deter-
mined on a FishereJohns apparatus and are uncorrected.
63.15 (63.55); H 4.85 (4.57). Yield 95.0%. M. p. 121e124 ꢀC. IR (KBr):
n
(CO) 1999 s,1946 s,1894 s, cmꢁ1. IR(CHCl3):
n(CO) 2007 s,1943 s,1909
s, cmꢁ1.1H-NMR (CDCl3 þ D2O, 300 MHz):
d/ppm: 7.64e7.25 [m, 20H,
(H5C6)2P(CH2)2P(C6H5)2]; 6.64 [t, 1H, Hm, eS(C6H4em-NH2),
JHeH ¼ 7.68 Hz]; 6.35 [d,1H, Ho, eS(C6H4em-NH2), JHoeHm ¼ 7.14 Hz];
6.22 [d, 1H, Hp, eS(C6H4em-NH2), JHmeHo ¼ 7.68 Hz]; 5.82 [s, 1H, Ho`,
4.1. General method for the synthesis of complexes (2)e(6)
Equimolar amounts of Mn(
h
5-C5H7)(CO)3, (1) and dppe were
eS(C6H4em-NH2)]; 3.73 [s, 2H, H , eS(C6H4em-NH2)]; 3.03 [t, 2H,
NH2
mixed in 100 mL of cyclohexane in a 250 mL round bottom flask
charged with a magnetic stirrer and previously purged with
nitrogen, the solution turned turbid yellow; since dppe is insoluble
in cyclohexane at room temperature. An equimolar amount of
mercaptan (RSH, R ¼ Ph, C6F5, m-NH2C6H4, p-NH2C6H4, HSCH2CH2
see below for amounts, reaction times and yields) was then added
and the mixture was set at reflux temperature. Samples were
HCH , Ph2PeCH2eCH2ePPh2, JCeP ¼ 5.55 Hz]; 2.59 [t, 2H, H
,
CH2
2
Ph2PeCH2eCH2ePPh2, JCeP ¼ 6.03 Hz]; 31P-NMR{1H} (CDCl3,
121.7 MHz): d d/ppm:
/ppm: 72.97 s. 13C{1H}-NMR (CDCl3, 75.6 MHz):
167.84 [s, Ci(N), eS(C6H4em-NH2)]; 132.54 [s Ci(S),-(SC6H4em-NH2)];
131.88 [s, Co, Ph2P(CH2)2PPh2, JCoeP ¼ 4.84 Hz] 130.96 [s, Cm, Ph2P
(CH2)2PPh2]; 130.32 [s, Cm(S), S(C6H4em-NH2)]; 129.87 [s, Co(S),
eSC6H4em-NH2]; 128.88 [s, Cp, Ph2P(CH2)2PPh2], 128.36 [s, Co`, eS
collected every 10 min for monitoring purposes (
n
(CO) IR pattern).
(C6H4em-NH2)]; 23.90 [d C , Ph2P(CH2)2PPh2, J
¼ 57:43 Hz].
CH2
CH2ꢁP
After 1e2 h the reaction was completed. The reaction was left to
reach room temperature. The solvent was eliminated under reduced
pressure remaining light yellow solids (complexes (2) and (3)) or
greenish-brown solids (complexes (4), (5), and (6)). The dry residue
was washed with hexane (3 ꢂ 10 mL) to eliminate unreacted (1). The
remaining material was dissolved in dichloromethane (ca. 20 mL)
and filtered via cannula to a Schlenk flask. Evaporation of dichloro-
methane under reduced pressured afforded complexes (2)e(6) as
fine powders. Crystallization in a dichloromethaneeMeOH solution
of (2), or in a toluene solution of (3) at ꢁ4 ꢀC afforded crystals suit-
able to conduct X-ray diffraction analyses. Crystallization from
dichloromethane at ꢁ4 ꢀC afforded crystals suitable of (4) and (5) to
conduct X-ray diffraction analyses.
FABþ MS (m/e): 661 [M]þ, 577 [M ꢁ 3CO]þ, 453 [M ꢁ 3CO ꢁ
SC6H4em-NH2]þ.
Complex fac-Mn(CO)3((SC6H4ep-NH2))(Ph2PCH2CH2PPh2-k
2-P)
(5). p-Aminothiophenol 2.43 mmol, 304 mg; (1) 2.43 mmol,
500 mg; dppe 2.43 mmol, 967 mg. Reaction time: 2 h. Anal. found
(calcd.): C 63.17 (63.55); H 4.15 (4.57). Yield 96.0%. M. p. 82e86 ꢀC. IR
(KBr):
n n(CO) 2009 s,
(CO) 2002 s, 1934 s, 1899 s, cmꢁ1. IR(CHCl3):
1944 s, 1907 s, cmꢁ1
.
1H-NMR (CDCl3 þ D2O, 300 MHz):
d/ppm:
7.65e7.37 [m, 20H, (H5C6)2P(CH2)2P(C6H5)2]; 7.25 [d, 2H, Ho(S), eS
(C6H4ep-NH2), JHoeHm ¼ 6.87 Hz]; 6.57 [d, 2H, Hm(S), eS(C6H4ep-
NH2), JHmeHo ¼ 7.7 Hz]; 3.33 [s, 2H, H , eS(C6H4ep-NH2)]; 3.00 [d,
NH2
2H, Ph2PeCH2eCH2ePPh2, JHeP ¼ 6.4 Hz]; 2.53 [d, 2H,
Ph2PeCH2eCH2ePPh2, JHeP ¼ 5.5 Hz]; 31P{1H}-NMR (CDCl3,
Complex
fac-Mn(CO)3(SPh)(Ph2PCH2CH2PPh2-k2-P,P0)
(2).
121.7 MHz): d d/
/ppm: 73.52 s. 13C{1H}-NMR (CDCl3, 75.6 MHz):
Phenyl mercaptan, 2.2 mmol, 247 mg; (1) 2.2 mmol, 462 mg; dppe
ppm:221.47 [s broad, CO]; 147.02 [s, Ci(N), eS(C6H4ep-NH2)]; 135.62
[t Ci(P), Ph2P(CH2)2PPh2, JCieP ¼ 23.0 Hz]; 133.86 [s, Co(S), SC6H4ep-
NH2]; 132.06 [d, Co(P), Ph2P(CH2)2ePPh2, JCoeP ¼ 34.3 Hz]; 129.89 [d,
Cm(P), Ph2PeCH2eCH2ePPh2, JCmeP ¼ 40.5 Hz]; 128.41 [d, Cp(P),
Ph2P(CH2)2PPh2, JCpeP ¼ 44.8 Hz]; 125.63 [s, Ci(S), eS(C6H4ep-
NH2)]; 115.30 [s, Cm(S), eS(C6H4ep-H2N)], 114.79 [s, Cm`(S), eS
2.2 mmol, 894 mg. Reaction time: 1 h. Anal. found (calcd.): C 65.32
(65.02); H 4.86 (4.52) Yield 94.0%, m.p. 158 ꢀC dec. IR (KBr):
n
(CO)
(CO) 2011 s, 1945 s 1910
d/ppm: 7.55 [d, 2H, Ho, eSPh,
1999 s, 1942 s, 1893 s cmꢁ1. IR (CHCl3):
s cmꢁ1 1H-NMR (CDCl3, 300 MHz):
n
.
JHeP ¼ 18.3 Hz]; 7.34 [S, broad, 20H, PPh2]: 6.77 [t, 2H, Hm, eSPh,
JHeH ¼ 9.09 Hz]; 6.69 [d, 2H, Hp, eSPh, JHeH ¼ 9.03 Hz]; 3.26 [d, 2H,
Ph2PCH2CH2PPh2, JHeP ¼ 7.68 Hz]; 2.60 [d, 2H, Ph2PCH2CH2PPh2,
(C6H4ep-H2N)]; 24.92 [t, C , PPh2(CH2)2PPh2; JCeP ¼ 21.5 Hz].
CH2
FABþ MS (m/e): 577 [M ꢁ 3CO]þ, 453 [M ꢁ 3CO ꢁ (SC6H4ep-H2N)]þ.
Complex fac-Mn(CO)3(SCH2CH2SH)(Ph2PCH2CH2PPh2-k2-P,P0) (6).
1,2-ethanedithiol 1.21 mmol, 114 mg; (1) 1.21 mmol, 250 mg; dppe
1.21 mmol, 483 mg. Reaction time: 1 h 15 min. Anal. found (calcd.): C
JHeP ¼ 8.04 Hz], 31P{1H}-NMR (CDCl3, 121.7 MHz):
d/ppm: 79.0 s.
d/ppm: 145.85 [t, Ci, Ph2P
13C{1H}-NMR (CDCl3, 75.6 MHz):
(CH2)2PPh2, JCieP ¼ 5.77 Hz]; 135.55 [t, Ci, eSPh, JCieP ¼ 17.80 Hz];
134.78 [s, Co, eSPh] 132.13 [d, Co, Ph2P(CH2)2PPh2, JCoeP ¼ 43.2 Hz];
130.07 [d, Cm, SPh, JCeP ¼ 35.60 Hz]; 128.57 [d, Cm, Ph2P(CH2)2PPh2,
JCeP ¼ 43.2 Hz]; 127.11 [s, Cp, Ph2P(CH2)2PPh2], 123.37 [s, Cp, eSPh];
58.92 (59.05); H 4.65 (4.64). Yield 85.0%. M. p. 125 ꢀC dec. IR (KBr):
(CO) 2001 s,1934 s 1897 s; cmꢁ1, IR(CHCl3):
(CO) 2010 s,1944 s,1907
s, cmꢁ1 1H-NMR (CDCl3, 300 MHz):
/ppm: 7.83e7.97 [m, 20H,
n
n
.
d
25.09 [t CCH , Ph2P(CH2)2PPh2, JCeP ¼ 21.62 Hz]. FABþ MS (m/e):
(H5C6)2P(CH2)2P(C6H5)2]; 3.75 [s broad, 2H , eSCH2CH2SH]; 3.16 [s
CH2
2
562 [M ꢁ 3CO]þ; 537 [M ꢁ SPh]þ; 453 [M ꢁ 3CO ꢁ SPh].
broad, 2H, Ph2PCH2CH2Ph2]; 2.75 [s broad, 2H, Ph2PCH2CH2Ph2]; 2.16

K.P. Salas-Martin et al. / Journal of Organometallic Chemistry 695 (2010) 2548e2556
2555
[s broad, HSH, SCH2CH2SH]; 1.85 [s broad, 2H , SCH2eCH2SH]. 31P
precipitate (dark brown material) the solvent was eliminated under
reduced pressure. The resulting product was washed with hexane
and crystallized from dichloromethane giving a yellow solid in
21.0%. Crystallization by diffusion of a dichloromethane solution of
(9) and hexane at ꢁ4 ꢀC afforded suitable crystals to accomplish an
X-ray diffraction analysis.
CH2
{1H}-NMR (CDCl3, 121.7 MHz):
d
/ppm: 73.11 s. 13C-NMR{1H} (CDCl3,
75.6 MHz): /ppm: 219.88 [s broad, CO]; 129.73 [broad, CPh, (H5C6)P
d
(CH2)2(C6H5)2]; 37.53 [broad, C , eSCH2CH2SH]; 25.19 [broad,
CH2
CCH , ePh2P(CH2CH2)PPh2]. FABþ MS (m/e): 537 [M ꢁ SCH2CH2SH]þ.
2
4.2. General method for the synthesis of complexes (7) and (8)
Complex [Mn2(CO)6(
dec. Anal. found (calcd.): C 29.92 (30.32); H 3.86 (3.56). IR (KBr):
(CO) 2024 w, 1986 s, 1864 s cmꢁ1. IR (CH2Cl2):
(CO) 2024 m, 1989 s,
1921 s, 1895 s, 1877 s cmꢁ1 1H-NMR (THF-d8, 300 MHz):
/ppm:
5.27 [s(a), Mn( -NH)Mn, ], 3.83[s broad, H4, -NH(CH2eCH2)NH2],
3.58 [ s broad, H, -NH(CH2eCH2)NH2 ], 2.98 [s broad, -NH
(CH2eCH2)NH2], 2.81 [s broad,
-NH(CH2eCH2)NH2]. 13C-NMR
(THF-d8, 75 MHz): /ppm: 229.78 - 217.57 [s broad, CO]; 57.72 [s,
NH(CH2eCH2)NH2]; 44.22 [s broad, -NH2(CH2eCH2)NH2].
m
-NH(CH2)2NH2-k2-N,N0)2] (9) M. p. 142 ꢀC
n
Complex (1) (1.0 mmol, 206.0 mg) was dissolved in 100 mL of
cyclohexane in a 250 mL round bottom flask with a magnetic stirrer
previously purged with nitrogen. Ethylenediamine was added in an
n
.
d
m
m
equimolar amount (1.0 mmol, 67
mercaptan was added (PhSH 1.0 mmol, 102
133 L) and the solution turned turbid. The temperature was raised
to reflux until the IR spectrum in the (CO) region remained
m
L). The corresponding
m
m
mL; C6F5SH 1.0 mmol,
m
m
d
m-
n
m
unchanged (see below for reaction times and yields). As the reac-
tion progressed an insoluble yellow material appeared. Reaction
monitoring was conducted taking aliquots and then eliminating the
cyclohexane and dissolving the sample in dichloromethane to run
4.4. 1H-NMR monitoring experiments
Formation of complex (3) was monitored by proton NMR.
15.4 mg (0.075 mmol) of (1) and 29.0 mg (0.075 mmol) of dppe
were dissolved in cyclohexane-d12, previously degassed in an NMR
the IR spectrum in the n(CO) region. At the reaction end the reaction
was allowed to reach room temperature and the solvent was
eliminated under reduced pressure. The yellow material obtained
after solvent evaporation was washed with hexane to remove
unreacted (1). The resulting material was dissolved in dichloro-
methane (20 mL), filtered through a cannula and the solvent
evaporated under reduced pressure remaining complexes (7) and
(8) as light yellow materials. Crystallization by diffusion of
a dichloromethane solution of (7) or (8) in hexane at ꢁ4 ꢀC afforded
crystals suitable to conduct X-ray diffraction analyses.
tube saturated with nitrogen; 10 mL (0.075 mmol) of C6F5SH were
added, heated to 75 ꢀC and recording a spectrum every 15 min.
Acknowledgements
The authors thank I. Chávez-Uribe, V. Gómez-Vidales, M. A.
Peña-Gonzáles, R. Patiño-Maya, L. Velasco-Ibarra, E. García-Ríos
and S. Hernández for technical assistance (Instituto de Química,
UNAM). M. R.-L. gratefully acknowledges a student grant from
CONACyT. N. Z.-V. expresses gratitude to CONACyT for funding of
this project through grant P47263-Q and PAPIIT (DGAPA-UNAM)
grant IN217706-2.
Complex fac-Mn(CO)3(SPh)(H2NCH2CH2NH2-k2-N,N0) (7) Reac-
tion time: 2 h. Anal. found (calcd.): C 42.53 (42.86); H 4.37 (4.25); N
8.71 (9.08). Yield 70.0%. M. p. 147e152 ꢀC. IR (KBr):
n
(CO) 2006 s,
(CO) 2015 s, 1919 s, 1897 s cmꢁ1. 1H-NMR
/ppm: 7.38 [s broad, Ho, eSPh], 7.00 [s broad,
1885 s cmꢁ1. IR (CH2Cl2):
(DMSO-d6, 300 MHz):
n
d
Hm, eSPh], 6.88 [s(a), Hp, eSPh], 4.69 [s broad, NH2(CH2)2NH2], 2.75
[s broad, NH2(CH2)2NH2], 2.42 [s broad, H, H*, NH2(CH2)2NH2]. 13C-
Appendix A. Supplementary material
NMR (DMSO-d6, 75 MHz): d/ppm: 223.54 [s broad, CO], 147.29
[s, Ci, eSPh]; 133.42 [s, Co, eSPh], 127.52 [s, Cm, eSPh]; 122.20 [s, Cp,
CCDC 778682e778688 contain supplementary crystallographic
data for (7), (8), (9), (2), (3), (4), and (5) resp. These data can be
obtained free of charge from The Cambridge Crystallographic Data
Centre via www.ccdc.cam.ac.uk/data_request/cif.
eSPh]. FABþ MS (m/e): 308, [M]þ; 224 [M ꢁ 3CO]þ.
Complex fac-Mn(CO)3(SC6F5)(H2NCH2CH2NH2-k2-N,N0) (8) Reac-
tion time: 13 h. Anal. found (calcd.): C 33.52 (33.18); H 2.46 (2.03).
Yield69.0%. m.p.160 ꢀCdec.IR(KBr):
IR (CH2Cl2):
300 MHz):
NH2(CH2)2NH2], 2.76 [s(a), H, H*, NH2H3(CH2)2NH2H3]. 13C-NMR
(CD2Cl2, 75 MHz): /ppm: 120.57 [s broad, Ci, eS(C6F5)]; 149.49 [d, Co,
n .
(CO)2024s,1929s,1884s cmꢁ1
n
(CO) 2022 s, 1926 s, 1906 s cmꢁ1. NMR-1H (CD2Cl2,
/ppm: 3.23 [s broad, NH2(CH2)2NH2], 2.88 [s broad,
References
d
[1] (a) L. Stahl, R.D. Ernst, Adv. Organomet. Chem. 55 (2008) 137;
(b) R.D. Ernst, Comments Inorg. Chem. 21 (1999) 285;
d
(c) R.D. Ernst, Chem. Rev. 88 (1988) 1255;
(d) P. Powell, Adv. Organomet. Chem. 26 (1986) 125.
JC4eF1 ¼228.3 Hz, eS(C6F5)], 138.17 [d, Cm, JC5eF2 ¼ 255.0 Hz, eS
(C6F5)], 130.23 [d, Cp, JC6eF3 ¼ 160.2 Hz, eS(C6F5)]. 19F-NMR (CD2Cl2,
[2] The reaction chemistry of nucleophiles towards pentadienyl complexes has
been extensively studied. Most reports deal with the reactivity of anionic
nucleophiles towards cationic pentadienyl complexes. Reaction chemistry
studies between neutral species have received the least attention. For reac-
tivity studies of anionic nucleophiles towards cationic pentadienyl complexes
see: (a) S. Chaudury, W.A. Donaldson, J. Am. Chem. Soc. 128 (2006) 5984 and
references therein;
3
282 MHz):
d
/ppm: ꢁ132.48 [d, Fo, JF1eF2 ¼ 21.9 Hz, eS(C6F5)];
3
ꢁ161.67 [t, Fm, JF1eF2eF3 ¼ 20.7 Hz, eS(C6F5)]; ꢁ164.33 [t, Fp,
3JF3eF2 ¼ 4.9 Hz, JF3eF1 ¼ 23.2 Hz, eS(C6F5)]. FABþ MS (m/e): 398,
4
[M]þ; 314 [M ꢁ 3CO]þ.
Attack of neutral nucleophiles on cationic pentadienyl complexes see: (b)
A. Hafner, J.H. Bieri, R. Prewo, W. von Philipsborn, A. Salzer, Angew. Chem., Int.
Ed. Engl. 22 (1983) 713;
4.3. Synthesis of complex [fac-Mn(CO)3(m -
-H2NCH2CH2NH-k2
N,N0)]2 (9)
Reactivity of anionic nucleophileeneutral pentadienyl complex see: (c)
B.J. Roell Jr., K.F. McDaniell, J. Am. Chem. Soc. 114 (1990) 9004;
Reactivity of neutral nucleophile and neutral pentadienyl complex see: (d)
M.A. Paz-Sandoval, R. Sánchez-Coyotzi, N. Zúñiga-Villarreal, R.D. Ernst,
A.M. Arif, Organometallics 14 (1995) 1044;
(e) M.A. Paz-Sandoval, P. Juárez-Saavedra, N. Zúñiga-Villarreal, M.J. Rosales-
Hoz, P. Joseph-Nathan, R.D. Ernst, A.M. Arif, Organometallics 11 (1992) 2467;
(f) N. Zúñiga-Villarreal, M.A. Paz-Sandoval, P. Joseph-Nathan, O. Esquivel,
Organometallics 10 (1991) 2616.
Complex (1) (1.0 mmol, 206.0 mg) was dissolved in 100 mL of
cyclohexane in a 250 mL round bottom flask with a magnetic stirrer
previously purged with nitrogen. Ethylenediamine was added
(8.0 mmol, 536 mL). The reaction mixture was heated to cyclo-
hexane reflux and maintained for 12 h. Samples were taken every
30 min for monitoring purposes. There was a change in color from
light yellow to amber and at the end of the reaction to dark red. The
reaction mixture was allowed to cool to room temperature after
which a brown precipitate was formed. After filtering off the
[3] (a) M. Reyes-Lezama, R.A. Toscano, N. Zúñiga-Villarreal, J. Organomet. Chem.
517 (1996) 19;
(b) M. Reyes-Lezama, H. Höpfl, N. Zúñiga-Villarreal, J. Organomet. Chem. 693
(2008) 987;

2556
K.P. Salas-Martin et al. / Journal of Organometallic Chemistry 695 (2010) 2548e2556
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materials for mononuclear complexes were used fac-Mn(CO)3(dppe)(E),
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[11] An
and IR (
h
3-Pentadienyl species and 1,4-pentadiene could be observed by 1H-NMR
n
(CO)); besides, an IR band at 1874 cmꢁ1 suggests the presence of the
acyl complex Mn(CO)3(COC6H4PhPCH2CH2PPh2) analogous to Mn(CO)
(COC6H4PhPCH2CH2PPh2)e(Ph2PCH2CH2PPh2):
(a) M. Laing, P.M. Treichel, J. Chem. Soc., Chem. Commun. (1975) 746;
(b) R.H. Reimann, E. Singleton, J. Organomet. Chem. 38 (1972) 113 In the present
case formation of Mn(CO)3(COC6H4PhPCH2CH2PPh2) can be accounted for by
ortho-metalation of one phenyl group of dppe. Hydrogen migration from the
metal center to the pentadienyl ligand would afford the coordinated 1,4-pen-
tadiene which would then be extruded by the other dppe phosphorus atom.
(c) P.M. Treichel, in: E.W. Abel, F.G.A. Stone, G. Wilkinson (Eds.), COMC I, vol. 3,
Pergamon Press, London, 1982 (Chapter 29).
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