Polynuclear selenido-carbonyl manganese complexes derived from tertiary phosphine selenides

Article abstract of DOI:10.1016/S0020-1693(03)00174-9

The reactions of some phosphine selenides with mononuclear and dinuclear manganese complexes have been investigated. The reactions of Cp′Mn(CO)₂(THF) (1) with bis(diphenylphosphino)ethane diselenide (dppeSe₂) affords [(Cp′Mn)₂(μ-Se) ₂(CO)₂(dppe)] (4), identified by spectroscopic techniques. Complex CpMn(CO)₂(THF) (2), by reacting with bis(diphenylphsphino) methane monoselenide (dppmSe) gives a variety of products, [(CpMn) ₂(μ-Se)₂(CO)₃(dppm)] (5), [CpMn(CO) ₂(dppm)] (6), [(CpMn)₂(CO)₄(μ-dppm)] (7), [CpMn(CO)₂(dppmSe)] (8) have been identified (Cp=η ⁵-C₅H₅, Cp′=η⁵-C ₅H₄Me, THF=tetrahydrofuran). Finally the reactions of [Mn₂(CO)₈(MeCN)₂] (3) with diphenylmethylphosphine selenide (dpmpSe) and triphenylphosphine selenide (tppSe) afford clusters with molecular formula [Mn₄(μ ₃-Se)₂(μ-CO)(CO)₁₄(dpmp)₂] (9) and [Mn₄(μ₃-Se)₂(μ-CO)(CO) ₁₄(tpp)₂] (10), respectively. The structure of 9 has been determined by X-ray diffraction methods.

Full text of DOI:10.1016/S0020-1693(03)00174-9

Inorganica Chimica Acta 356 (2003) 187ꢀ192
/
www.elsevier.com/locate/ica
Polynuclear selenidoꢀ
/
carbonyl manganese complexes derived from
tertiary phosphine selenides
Daniele Belletti, Claudia Graiff, Chiara Massera, Roberto Pattacini, Giovanni Predieri,
Antonio Tiripicchio *
Dipartimento di Chimica Generale ed Inorganica, Chimica Analitica, Chimica Fisica, Universita` di Parma, Parco Area delle Scienze 17/A,
I-43100 Parma, Italy
Received 11 March 2003; accepted 16 March 2003
Dedicated to Professor Joao J.R. Frau´sto da Silva’s career on the occasion of his retirement
˜
Abstract
The reactions of some phosphine selenides with mononuclear and dinuclear manganese complexes have been investigated. The
reactions of Cp?Mn(CO)2(THF) (1) with bis(diphenylphosphino)ethane diselenide (dppeSe2) affords [(Cp?Mn)2(m-Se)2(CO)2(dppe)]
(4), identified by spectroscopic techniques. Complex CpMn(CO)2(THF) (2), by reacting with bis(diphenylphsphino)methane
monoselenide (dppmSe) gives a variety of products, [(CpMn)2(m-Se)2(CO)3(dppm)] (5), [CpMn(CO)2(dppm)] (6), [(CpMn)2(CO)4(m-
dppm)] (7), [CpMn(CO)2(dppmSe)] (8) have been identified (Cpꢁ
/
h5-C5H5, Cp?ꢁ
/
h5-C5H4Me, THFꢁ
/
tetrahydrofuran). Finally
the reactions of [Mn2(CO)8(MeCN)2] (3) with diphenylmethylphosphine selenide (dpmpSe) and triphenylphosphine selenide (tppSe)
afford clusters with molecular formula [Mn4(m3-Se)2(m-CO)(CO)14(dpmp)2] (9) and [Mn4(m3-Se)2(m-CO)(CO)14(tpp)2] (10),
respectively. The structure of 9 has been determined by X-ray diffraction methods.
# 2003 Elsevier Science B.V. All rights reserved.
Keywords: Selenido complexes; Manganese complexes; Crystal structures; Cluster complexes
1. Introduction
Tertiary phosphine chalcogenides R3PE (Eꢁ
Te) have served as useful starting compounds for the
synthesis of transition metal clusters containing bridging
chalcogenido ligands by reaction with metal carbonyl
complexes [1]. This simple preparative method takes
More recently, we have synthesized by this method
bimetallic selenido clusters, starting from bimetallic
carbonyl clusters [3]. Furthermore, we have found that
the use of heterocyclic phosphine selenides in these
processes affords selenido clusters containing coordi-
/
S, Se or
nated heterocyclic fragments derived from Pꢀ
/
C bond
cleavages [4].
advantage of the reactivity of the PÄ
/
E bond which
We have now reacted different phosphine selenides
with three manganese carbonyl complexes, namely
[Cp?Mn(CO)2(THF)] (1), [CpMn(CO)2(THF)] (2)
makes easy the formation of phosphine-substituted
chalcogenide clusters through oxidative transfer of
chalcogen atoms to low-valent metal species.
(Cpꢁ
furan) and [Mn2(CO)8(NCMe)2] (3) with the aim to
produce new phosphine-substituted selenidoꢀcarbonyl
manganese derivatives.
/
h5-C5H5, Cp?ꢁ
/
h5-C5H4Me, THFꢁ
/tetrahydro-
In recent years, this synthetic procedure has been
intensively used by our group obtaining a variety of
/
selenidoꢀ
/
carbonyl, transition metal clusters of different
Fe or Ru) [2].
nuclearity starting from [M3(CO)12] (Mꢁ
/
As regards manganese molecular clusters and com-
plexes containing selenido ligands, there has been little
work previously reported, mainly regarding reactions
starting from polyselenide anions [5], diorganyl disele-
nides [6] and elemental selenium [7].
* Corresponding author. Tel.: ꢂ
905-557.
E-mail address: tiri@unipr.it (A. Tiripicchio).
/
39-0521-905-418; fax: ꢂ39-0521-
/
0020-1693/03/$ - see front matter # 2003 Elsevier Science B.V. All rights reserved.
doi:10.1016/S0020-1693(03)00174-9

188
D. Belletti et al. / Inorganica Chimica Acta 356 (2003) 187ꢀ192
/
2. Results and discussion
ganese atoms, has already been reported by Herrmann
et al. [8]. On the basis of these data we propose for
compound 4 the structure shown in Scheme 1.
The reactions between manganese carbonyls and
tertiary phosphine chalcogenides were carried out at
moderate temperatures by using the labile intermediates
Cp?Mn(CO)2(THF) (1), CpMn(CO)2(THF) (2), gener-
ated by photochemical activation, and Mn2(CO)8-
(MeCN)2 (3) produced by decarbonylation with
Me3NO, respectively, from the parent carbonyls.
From the reactions of 2 with dppmSe, one green and
three yellow products were obtained, namely [(CpMn)2-
(m-Se)2(CO)3(dppm)] (5), [CpMn(CO)2(dppm)] (6),
[(CpMn)2(CO)4(m-dppm)] (7), [CpMn(CO)2(dppmSe)]
(8), respectively. Their structures have been proposed
on the basis of their characterization data and by
comparison with those observed for compound 5 and
for literature [9] (see Scheme 2).
2.1. Reactions of 1 and 2 with diphosphines selenides
In all the IR spectra of the different products it
possible to recognize in the 2000ꢀ
1850 cmꢃ1 region the
signals due to the stretching of the carbonyl groups. In
particular for compound 5 the three main bands are at
2004 and 1946 cmꢃ1, values quite similar to those of
compound 4. The 31P NMR spectrum shows two
/
The reaction between 1 and bis(diphenylphosphi-
no)ethane diselenide (dppeSe2) affords, as the main
product, a green compound identified as the 36 electron
dinuclear species [(Cp?Mn)2(m-Se)2(CO)2(dppe)] (4), for-
mulated on the basis of elemental and mass-spectro-
scopic data.
doublets with no satellites at d 85.3 and d ꢀ25.9,
/
indicating that the phosphine acts as a monodentate
ligand coordinating the metal through one P atom
(positive chemical shift value) while the latter P atom
remains free. Considering these experimental evidences
and the number of electrons necessary for the manga-
nese to reach the total count of 18 electrons, also in this
The IR spectrum of 4 exhibits two bands at 1999 and
1944 cmꢃ1, due to the stretching modes of geminal
carbonyls; they are at higher frequencies with respect to
parent derivative 1 (1927, 1851 cmꢃ1), in agreement
with the higher formal oxidation state of the metal in 4.
The 31P NMR spectrum of 4, shows a singlet at d 88
ppm, indicating that the two phosphorous atoms are
equivalent; no satellites (which would be due to the
presence of the selenium on the phosphine) are present,
so the phosphine is directly coordinated on the metal
and having lost the selenium atoms. The presence of the
selenium in the molecule has been evidenced by mass
spectrometry, as the isotopic pattern of this element is
characteristic and has been compared with calculated
data.
The most important fragments in the NICI spectrum
are: [(Cp?Mn)2Se]ꢃ (m/z 348), [{(Cp?)2Mn2(CO)2Se]ꢃ
(m/z 404) and [(Cp?Mn)2Se2]ꢃ (m/z 427) which indicate
the presence of a dimeric species with selenium atoms
bridging the two metals (see Scheme 1).
The existence of the m/z 348 and m/z 404 fragments is
also supported by data reported in the literature: in fact
the X-ray crystal structure of [{Cp*Mn(CO)2}2Te],
(Cp*ꢁ
/
h5-C5Me5) in which tellurium bridges two man-
Scheme 1.
Scheme 2.

D. Belletti et al. / Inorganica Chimica Acta 356 (2003) 187ꢀ
/192
189
case a dimeric structure with two bridging selenium
atoms can be proposed.
FTIR spectrum of 10 is quite similar to that of 9. All the
reactions are strongly selective, the products being air
In the case of the three yellow compounds, as already
indicated by the colour, the manganese has not been
oxidated by the selenium atom; in particular in com-
pound 6 the 31P NMR shows a spectrum with two signal
stable and obtainable in high yields (80ꢀ90%). The
/
reaction mechanism could involve the formation of
[{Mn2(m-Se)(CO)8(PR3)] as intermediate product, result-
ing from of the primary attack of the phosphine
selenide. This dinuclear intermediate could then undergo
a self-condesation that leads to the formation of the
final product with loss of a carbonyl molecule.
The same reactions, carried out under the same
conditions with R3PS replacing R3PSe, proceed with
the progressive decomposition of 3, without the forma-
tion of observable sulfido carbonylic molecular species.
This behaviour could be explained considering that
tertiary phosphine sulfides are less reactive than the
correspondent selenides, a higher temperature is re-
at d 85.5 and d ꢃ25.9, with no satellites: also in this
/
case the coordination of the phosphine is through one P
atom while the latter remains non-coordinated, giving a
monomeric compound in which the metal atom is
surrounded by two carbonyl groups and the dppm
ligand.
In compound 7 the situation is different; in this case
31P NMR shows a sharp singlet with no satellites at d
87.6: the two P atoms are equivalent and both are bound
to the metal. These data, together with the IR spectrum
which shows two bands at 1928 and 1862 cmꢃ1, the
same absorptions of the intermediate compound 2,
suggest that the manganese atom coordinates two
carbonyl groups. The structure is likely to be that of a
dimer in which the dppm bridges two metals. This
hypothesis is also supported by the comparison of these
spectroscopic data with those of another compound
reported in the literature, namely the tetracarbonyl-(m2-
dppm)-(m2-h5-fulvalene)dimanganese [10]. The IR spec-
trum for this compound recorded at the solid state
shows two bands at 1927 and 1863 cmꢃ1. The 31P NMR
presents a singlet at d 87.26; the slight differences
between the two compounds are due to the rigidity
given by the fulvalene to the system.
quested to activate the PÄ
/
S bond.
The crystal structure of the dichloromethane solvate
of 9 has been determined by X-ray diffraction. A view of
the structure of 9 is shown in Fig. 1. Selected bond
distances and angles are given in Table 1.
The complex, having an approximate C2 symmetry,
consists of a Mn4Se2 core with two Mn and two Se
atoms in a butterfly configuration, the two Mn atoms
˚
Mn4ꢁ2.7029(8) A]
occupying the hinge sites [Mn3ꢀ
/
/
and the two Se atoms the wings sites [Mnꢀ
/
Se bond
2.4784(7) A]. Both Mn3
˚
lengths in the range 2.4510 (12)ꢀ
/
and Mn4 are bound to three terminal carbonyl groups,
while a fourth carbonyl asymmetrically bridges them
˚
C5ꢁ2.159(4) and 2.015(4) A,
[Mn3ꢀ
/
C5 and Mn4ꢀ
/
/
The 31P NMR spectrum of compound 8 shows two
signals both at positive values of chemical shift, one of
them is accompanied by two satellites due to the
coupling with 77Se. This suggests a h1 coordination of
the phosphine through the P atom, which is at higher
respectively]. Each of two Se atoms is also attached to
another Mn atom of an octahedral Mn(CO)4(dpmp)
group in which a P atom from the phosphine is
coordinated to the Mn atom [Mn1ꢀ
/
P1 and Mn2ꢀ
2.3808(12) and 2.3697(12) A, respectively], in
such a way that the Se atoms triply bridge three Mn
atoms. It is to note that the SeꢀMn bond lengths
/
˚
P2ꢁ
/
chemical shift values, while the PÄ
/Se group remains
non-coordinated.
/
2.2. Reaction of 3 with phosphine selenides
Recently, the synthesis and the structure of the
simplest chalcogenido manganese cluster, [Mn2(m2-
S)2(CO)7], have been reported [11]. The same paper
describes also the synthesis and the structure of the
tetranuclear cluster [Mn4(m3-S)2(m-CO)(CO)14(dmpp)2],
obtained as a product of the reaction of Mn2(m2-
S)2(CO)7
with
dimethylmethylphenylphosphine
(dmpp). The reactions of 3 with diphenylmethylpho-
sphine selenide (dpmpSe) and triphenylphosphine sele-
nide (tppSe) afford analogous tetranuclear clusters of
formula [Mn4(m3-Se)2(m-CO)(CO)14(dpmp)2] (9) and
[Mn4(m3-Se)2(m-CO)(CO)14(tpp)2] (10), respectively.
The 31P NMR spectra of 9 and 10 show broad singlets
at d 29.0 and d 45 ppm, respectively. The bridging
carbonyl stretching band is clearly distinguishable at
1867 cmꢃ1 in the FTIR spectrum in the solid state.
Fig. 1. View of the molecular structure of [Mn4(m3-Se)2(m-
CO)(CO)14(dpmp)2] (9) together with the atomic numbering system.
Thermal ellipsoids are drawn at 30% probability level.

190
D. Belletti et al. / Inorganica Chimica Acta 356 (2003) 187ꢀ192
/
Table 1
1H (300 MHz), 31P (81.0 MHz, 85%-H3PO4 as external
reference) NMR spectra (CDCl3 solutions) were re-
corded on Bruker instruments, AC 300 (1H) and CXP
200 (31P).
˚
List of selected bond lengths (A) and bond angles (8) for 9
Bond lengths
Mn(1)ꢀ
Mn(1)ꢀ
Mn(2)ꢀ
Mn(2)ꢀ
Mn(3)ꢀ
/
P(1)
Se(1)
P(2)
2.3808(12) Mn(3)ꢀ
2.5339(12) Mn(3)ꢀ
2.3697(12) Mn(4)ꢀ
2.5189(10) Mn(4)ꢀ
/
Se(1)
Mn(4)
Se(2)
Se(1)
2.4572(10)
2.7029(8)
2.4735(10)
2.4784(7)
/
/
/
/
/
Se(2)
Se(2)
/
/
2.4510(12)
3.2. Reaction of 1 with dppeSe2
Bond angles
P(1)ꢀMn(1)ꢀ
P(2)ꢀMn(2)ꢀ
Se(2)ꢀ
Se(2)ꢀ
Se(1)ꢀ
Se(2)ꢀ
Se(2)ꢀ
Se(1)ꢀ
/
/
Se(1)
82.94(3)
86.80(4)
75.47(2)
Mn(3)ꢀ
Mn(3)ꢀ
Mn(4)ꢀ
Mn(3)ꢀ
Mn(3)ꢀ
Mn(4)ꢀ
Mn(4)ꢀ
/
Se(1)ꢀ
Se(1)ꢀ
Se(1)ꢀ
Se(2)ꢀ
Se(2)ꢀ
Se(2)ꢀ
C(5)ꢀ
/
Mn(4)
66.41(2)
dppeSe2 (511 mg, 0.92 mmol) dissolved in 50 ml of
THF was added to a concentrated solution of 1 (50 ml,
0.92 mmol). The mixture was stirred for 3 h till the
change of the colour from red to green, and then the
solution was evaporated to dryness. The green rough
solid product was separated and purified by TLC on
/
/Se(2)
/
/
Mn(1) 122.25(2)
Mn(1) 122.94(4)
/
Mn(3)ꢀ
Mn(3)ꢀ
Mn(3)ꢀ
Mn(4)ꢀ
Mn(4)ꢀ
Mn(4)ꢀ
/Se(1)
/
/
/
/Mn(4) 57.11(3)
/
/
Mn(4)
66.58(3)
/
/
Mn(4) 57.17(2)
74.69(4)
/
/
Mn(2) 120.92(4)
Mn(2) 122.12(3)
/
/Se(1)
/
/
/
/Mn(3) 56.31(4)
/
/
Mn(3)
80.63(13)
/
/Mn(3) 56.42(2)
silica, using CH2Cl2ꢀhexane (1:1) as eluent. The green
/
compound [(Cp?Mn)2(m-Se)2(CO)2(dppe)] (4) was sepa-
rated in modest yield (20%). FTIR (CH2Cl2, cmꢃ1):
involving the external Mn atoms are much longer than
those involving the Mn atoms of the hinge [Mn1ꢀSe1
2.5339(12) and 2.5189(10) A, respec-
1999s, 1944vs. MS-NICI, m/z (%): 839 (28), [(Cp?(ꢀ
/
/
Me))(Cp?)Mn2Se2(dppe) (CO)]ꢃ; 427 (88), [(Cp?)2Mn2-
Se2]ꢃ; 404 (62), [(Cp?)2Mn2Se(CO)2]ꢃ; 348 (48),
[(Cp?)2Mn2Se]ꢃ Anal. Found: C, 54.68; H, 4.10. Calc.
for Mn2Se2P2C40O2H36: C, 54.8; H, 4.3%. 31P{1H}
NMR (CDCl3): d 88s.
˚
and Mn2ꢀ
tively].
The structure of 9, as pointed out above, is strictly
comparable to that of [Mn4(m3ꢀS)2(m-CO)(CO)14-
(dmpp)2], in which the MnꢀMn hinge is shorter
/
Se2ꢁ
/
/
/
˚
[2.6356(16) A] and the bridging carbonyl is symmetric
[11].
3.3. Reaction of 2 with dppmSe
dppmSe (454 mg, 0.98 mmol) dissolved in THF was
added to a concentrated solution of 2 (50 ml, 0.98
mmol). The solution was then stirred for 3 h, till the
complete change of the colour from red to green, and
then evaporated to dryness. The green product was
3. Experimental
3.1. General remarks
The starting reagents, elemental selenium and sulfur,
KSeCN, [CpMn(CO)3], [Cp?Mn(CO)3], Mn2(CO)10,
Me3NO, and all the phosphines were pure commercial
products (Aldrich and Fluka) and were used as received.
Selenido phosphines tppSe [12], dppmSe2 [13] dppmSe
[14] were synthesized according to the literature proce-
dure using KSeCN, dpmpSe was synthesized by reaction
of diphenylmethyl phosphine with elemental selenium at
70 8C under nitrogen atmosphere for 5 h (yield 95%).
Cp?Mn(CO)2(THF) (1), CpMn(CO)2(THF) (2) [15] and
[Mn2(CO)8(MeCN)2] (3) [16] were prepared from the
parent carbonyls according to the literature.
The solvents (C. Erba) were dried and distilled by
standard techniques before use. All manipulations (prior
to the TLC separations) were carried out under dry
nitrogen by means of standard Schlenk-tube techniques.
Elemental (C, H, N) analyses were performed with a
Carlo Erba EA 1108 automated analyzer. IR spectra
(KBr discs or CH2Cl2 solutions) were recorded on a
Nicolet 5PC FT and a Nicolet ‘Nexus’ spectrometers.
Mass spectra were recorded ‘flow injection’ on a LC-MS
integrated system equipped with Particle Beam
separated and purified by TLC on silica, using CH2Cl2ꢀ
/
hexane (1:1) as eluent. Four main compounds (one
green and three yellow) were separated and recognized
to be [(CpMn)2(m-Se)2(CO)3(dppm)] (5), [CpMn(CO)2-
(dppm)] (6), [(CpMn)2(CO)4(m-dppm)] (7), [CpMn-
(CO)2(dppmSe)] (8), respectively, through IR spectro-
scopy and 31P{1H} NMR.
5: FTIR (CH2Cl2, n(CO), cmꢃ1): 2004w, 1946w.
Anal. Found: C, 51.5; H, 3.6. Calc. for Mn2Se2P2-
C38O3H30: C, 52.79; H, 3.47%. 31P{1H} NMR (CDCl3):
d 85.3d, ꢃ25.9d, J(P,P) 68 Hz.
/
6: FTIR (CH2Cl2, n(CO), cmꢃ1): 1929m, 1861m.
Anal. Found: C, 61.5; H, 4.3. Calc. for MnSeP2-
C32O2H26: C, 60.20; H, 4.08%. 31P{1H} NMR
(CDCl3): d 85.5d, ꢃ25.85d, J(P,P) 72 Hz.
/
7: FTIR (CH2Cl2, n(CO), cmꢃ1): 1928m, 1862m.
Anal. Found: C, 60.1; H, 3.6. Calc. for Mn2P2C39O4H30:
C, 63.77; 4.08%. 31P{1H} NMR (CDCl3): d 87.6s
8: FTIR (CH2Cl2, n(CO), cmꢃ1): 1928m, 1859m.
Anal. Found: C, 68.4; H, 4.3. Calc. for MnP2C32O2H26:
C, 68.71; H, 4.65%. 31P{1H} NMR (CDCl3): d 87.8d,
23.8d, J(P,P) 20 Hz, J(P,Se) 736 Hz.
HewlettꢀPackard 59980B and H. P. 5989A MS engine
/

D. Belletti et al. / Inorganica Chimica Acta 356 (2003) 187ꢀ
/192
191
3.4. Synthesis of [Mn4(m3-Se)2(m-
CO)(CO)14(dpmp)2] (9)
Table 2
Crystal data and structure refinement for compound 9×
/CH2Cl2
Formula
Mn4Se2P2O15C41H26
×
/
CH2Cl2
A toluene solution of [Mn2(CO)8(MeCN)2] (3) (300
mg, 0.72 mmol) and dpmpSe (201 mg, 0.72 mmol) was
stirred at 50 8C for 1 h under a nitrogen atmosphere.
The brown solution was evaporated to dryness yielding
a brown residue which was redissolved in a small
amount of dichloromethane. TLC separation on silica,
Formula weight
Crystal system
Space group
1283.16
monoclinic
P21/c
Unit cell dimensions
˚
a (A)
˚
19.697(3)
15.057(5)
16.667(5)
94.81(5)
4926(2)
4
b (A)
˚
c (A)
using a CH2Cl2ꢀpetroleum ether (1:1) mixture as eluent,
/
b (8)
3
˚
V (A )
yielded a brown band containing [Mn4(m3-Se)2(m-
CO)(CO)14(dpmp)2] (9) (yield 80%). Purification by
Z
Dcalc (g cmꢃ3
F(000)
)
1.730
220
27.18
crystallization (from a CH2Cl2ꢀMeOH mixture at 5 8C
/
m (cmꢃ1
)
for some days) gave crystals suitable for X-ray analysis.
FTIR (CH2Cl2, n(CO), cmꢃ1): 2078m, 2064s 2014vs,
1985sh, 1962m, 1932s. FTIR (KBr, n(CO), cmꢃ1):
2078s, 2066s, 2007vs, 1959s, 1931vs, 1911s, 1867w.
Anal. Found: C, 42.5; H, 2.0. Calc. for Mn4Se2P2-
C41O15H26: C, 41.08; H, 2.17%. 31P{1H} NMR (CDCl3):
d 29.0 br, 1H NMR (CDCl3): d 2.28 (t, 6 H, CH3,
Reflections collected and unique
Observed reflections [I ꢀ2s(I)]
Parameters
37750, 13630 [Rint
6751
606
ꢁ0.0494]
/
/
Final R indices [I ꢀ
/
2s(I)] a
R1ꢁ/0.0365, wR2ꢁ
/0.0662
R indices (all data) a
R1ꢁ/0.1051, wR2ꢁ
/0.0782
a
R1ꢁ
/
SjjFojꢃ
/
jFcjj/SjFoj; wR2ꢁ
/
[S[w(Fo2ꢃFc2)2]/S[w(Fo2)2]]1/2
.
/
1J(H,P)ꢁ
/
7.8 Hz), d 7.3ꢀ7.8 (m, 20 H, Ph).
/
final cycles of refinement a weighting scheme wꢁ
/1/
[s2Fo2ꢂ(0.0304P)2] where Pꢁ(Fo2ꢂ2Fc2)/3, was used.
/
/
/
3.5. Synthesis of [Mn4(m3-Se)2(m-CO)(CO)14(tpp)2]
(10)
Using the method described previously, [Mn4(m3-
Se)2(m-CO)(CO)14(tpp)2] was prepared (yield 90%)
from 300 mg (0.72 mmol) of 3 and 247 mg of tppSe.
The product was recognized by comparison of its
spectroscopical data with those observed for [Mn4(m3-
Se)2(m-CO)(CO)14(dpmp)2] (10). FTIR (CH2Cl2, d(CO),
cmꢃ1): 2078m, 2064s 2014vs, 1985sh, 1962m, 1932s.
Anal. Found: C, 45.5; H, 2.1. Calc. for Mn4Se2P2-
C51O15H30: C, 46.30; H 2.26% 31P{1H} NMR (CDCl3):
d 45.05.
4. Supplementary material
The supplementary material for the structures in-
cludes the lists of atomic coordinates for the non-H
atoms, of calculated coordinates for the hydrogen
atoms, of anisotropic thermal parameters and complete
lists of bond lengths and angles. Crystallographic data
for the structural analysis have been deposited with the
Cambridge Crystallographic Data Centre, CCDC No.
205586. Copies of this information may be obtained free
of charge from The Director, CCDC, 12 Union Road,
3.6. Crystal structure determination of complex 9×
/
Cambridge, CB2 1EZ, UK (fax: ꢂ44-1223-336-033;
e-mail: deposit@ccdc.cam.ac.uk or www: http://
www.ccdc.cam.ac.uk).
/
CH2Cl2
In the crystals of 9 dichloromethane molecules of
solvation were found. The intensity data of 9×CH2Cl2
/
were collected at room temperature on a Bruker AXS
Smart 1000 single crystal diffractometer equipped with
an area detector using a graphite monochromated Mo
Ka radiation. Crystallographic and experimental details
for the structure are summarized in Table 2. A correc-
tion for absorption was made using the Bruker software
packing. The structure was solved by Patterson and
Fourier methods and refined by full-matrix least-squares
procedures (based on Fo2) (SHELX-97) [17] first with
isotropic thermal parameters and then with anisotropic
thermal parameters in the last cycles of refinement for
all the non-hydrogen atoms. The hydrogen atoms were
introduced into the geometrically calculated positions
and refined riding on the corresponding parent atoms
excepting for the hydrogen atoms of the solvent. In the
Acknowledgements
Financial support from the Ministero dell’Universita`
e della Ricerca Scientifica e Tecnologica (Rome, Cofin
2000) is gratefully acknowledged. The facilities of the
Centro Interdipartimentale di Misure ‘G. Casnati’
(Universita` di Parma) were used to record the NMR
and mass spectra.
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