Reactions of Co2(CO)8 and of Co2(CO)6L (L = 3-pentyn-1-ol, 1,4-butyn-diol or 2-methyl-3-butyn-2-ol) with 2(diphenylphosphino)ethyl-trietoxysilane and tris(hydroxymethyl)phosphine for applications to new sol-gel materials

Article abstract of DOI:10.1016/j.jorganchem.2009.08.040

The complex Co₂(CO)₆[μ-η²-(H₃CC{triple bond, long}CCH₂CH₂OH)] (1) with the ligand 3-pentyn-1-ol (pol) has been synthesized following established procedures. Its structure has been determined by X-ray analysis. The complex Co₂(CO)₆(mbo) (mbo = 2-methyl-3-butyn-2-ol, HC{triple bond, long}CC(CH₃)₂OH), (3), along with the already known Co₂(CO)₆(bud) (bud = 1,4-butyn-diol, HOCH₂C{triple bond, long}CCH₂OH) (2), and Co₂(CO)₈ were reacted with 2(diphenylphosphino)ethyl-triethoxysilane [Ph₂PCH₂CH₂Si(OCH₂CH₃)₃] (dpts) and tris(hydroxymethyl)phosphine [P(CH₂OH)₃] (thp). With dpts, mono- and di-substituted complexes were obtained: these were characterized by analytical and spectroscopic techniques. The structures of Co₂(CO)₆(dpts)₂ (5) and of Co₂(CO)₄(pol)(dpts)₂ (8) have been determined by X-ray analysis. Complex (1) was reacted with 3-(triethoxysilyl)propyl isocyanate [(H₃CCH₂O)₃Si(CH₂)₃NCO] (tsi): the new complex Co₂(CO)₆[H₃CC{triple bond, long}CCH₂CH₂OC({double bond, long}O)NH(CH₂)₃Si(OCH₂CH₃)₃] (9) was obtained and spectroscopically characterized. The complex has also been reacted with tetraethyl orthosilicate (teos); a new inorganic-organometallic material was obtained. Complex (5) has been grafted on the mesoporous material SBA-15. The hybrid inorganic-organometallic materials obtained have been characterized by inductively coupled plasma-mass spectrometry (ICP-MS), infrared spectroscopy (FT-IR) under vacuum conditions, X-ray diffraction (XRD) and scanning electron microscopy coupled to EDS probe (SEM-EDS).

Full text of DOI:10.1016/j.jorganchem.2009.08.040

Journal of Organometallic Chemistry 694 (2009) 4241–4249
Contents lists available at ScienceDirect
Journal of Organometallic Chemistry
journal homepage: www.elsevier.com/locate/jorganchem
Reactions of Co2(CO)8 and of Co2(CO)6L (L = 3-pentyn-1-ol, 1,4-butyn-diol
or 2-methyl-3-butyn-2-ol) with 2(diphenylphosphino)ethyl-trietoxysilane
and tris(hydroxymethyl)phosphine for applications to new sol–gel materials
a,
a
Fabio Carniato a, Giorgio Gatti a, Giuliana Gervasio b, Domenica Marabello b, , Enrico Sappa , Andrea Secco
*
*
a Dipartimento di Scienze e Tecnologie Avanzate, Centro Interdisciplinare Nano-Sistemi, Università del Piemonte Orientale, Via Teresa Michel 11, I-15100 Alessandria, Italy
b Dipartimento di Chimica IFM, Università di Torino, Centro Interdipartimentale di Cristallografia Diffrattometrica CrisDi, via Pietro Giuria 7, I-10125 Torino, Italy
a r t i c l e i n f o
a b s t r a c t
The complex Co2(CO)6[l-g
2-(H3CC„CCH2CH2OH)] (1) with the ligand 3-pentyn-1-ol (pol) has been syn-
Article history:
Received 15 July 2009
Received in revised form 29 August 2009
Accepted 31 August 2009
Available online 4 September 2009
thesized following established procedures. Its structure has been determined by X-ray analysis. The com-
plex Co2(CO)6(mbo) (mbo = 2-methyl-3-butyn-2-ol, HC„CC(CH3)2OH), (3), along with the already known
Co2(CO)6(bud) (bud = 1,4-butyn-diol, HOCH2C„CCH2OH) (2), and Co2(CO)8 were reacted with 2(diphen-
ylphosphino)ethyl-triethoxysilane [Ph2PCH2CH2Si(OCH2CH3)3] (dpts) and tris(hydroxymethyl)phosphine
[P(CH2OH)3] (thp). With dpts, mono- and di-substituted complexes were obtained: these were character-
ized by analytical and spectroscopic techniques. The structures of Co2(CO)6(dpts)2 (5) and of Co2(CO)4-
(pol)(dpts)2 (8) have been determined by X-ray analysis.
Complex (1) was reacted with 3-(triethoxysilyl)propyl isocyanate [(H3CCH2O)3Si(CH2)3NCO] (tsi): the
new complex Co2(CO)6[H3CC„CCH2CH2OC(@O)NH(CH2)3Si(OCH2CH3)3] (9) was obtained and spectro-
scopically characterized. The complex has also been reacted with tetraethyl orthosilicate (teos); a new
inorganic–organometallic material was obtained. Complex (5) has been grafted on the mesoporous mate-
rial SBA-15. The hybrid inorganic–organometallic materials obtained have been characterized by induc-
tively coupled plasma-mass spectrometry (ICP-MS), infrared spectroscopy (FT-IR) under vacuum
conditions, X-ray diffraction (XRD) and scanning electron microscopy coupled to EDS probe (SEM–EDS).
Ó 2009 Elsevier B.V. All rights reserved.
Keywords:
Cobalt carbonyls
Functionalized alkynes
Triethoxysilyl ligands
Sol–gel inorganic–organometallic materials
Molecular structure
1. Introduction
a consequence, products different from those expected are ob-
tained, usually in low yields [7]. More recently, however, we found
Hybrid inorganic–organic sol–gel materials are currently syn-
thesized and used for example as a new class of heterogeneous cat-
alysts [1,2]. Some silica-based inorganic–organometallic materials
are also known; for example metal carbonyl clusters substituted
with alkynic ligands containing OH functionalities or Si(OCH2CH3)3
groups can be grafted to silica-based inorganic materials [3]. These
syntheses are however made difficult because of exchange reac-
tions between the coordinated alkynols and the sol–gel materials
and mostly because several alkynols undergo loss of their function-
alities when reacted with iron [4] or ruthenium [5] carbonyls. We
have therefore attempted the synthesis of new ligands by reacting
that 2(diphenylphosphino)ethyl-triethoxysilane (dpts) reacts with
Ru3(CO)12 forming the substituted complexes Ru3(CO)12ꢀnLn
[L = Ph2P(CH2)2Si(OCH2CH3)3; n = 1,2] in high yields and that these
complexes can be easily grafted to the mesoporous silica materials
SBA-15 and MCM-41 [9].
Here we report on the reaction of Co2(CO)8 with 3-pentyn-1-ol
(pol) which had not been previously described: we obtained very
high yields of the expected Co2(CO)6[l-g
2-(H3CC„CCH2CH2OH)]
(1) whose structure has been determined by X-ray analysis. Com-
plex (1) was reacted with 3-(triethoxysilyl)propyl isocyanate (tsi)
and with tetraethoxysilane (teos); the product of the reaction with
tsi, Co2(CO)6[H3CC„CCH2CH2OC(@O)NH(CH2)3Si(OCH2CH3)3], (9)
was characterized by analytical and spectroscopic techniques.
The material obtained with teos was also characterized by solid-
state spectroscopies.
The reactions of Co2(CO)8, Co2(CO)6L (L = pol, (1), L = bud
(1,4-butyn-diol, HOCH2C„CCH2OH), (2), L = mbo (2-methyl-3-
butyn-2-ol, HC„CC(CH3)2OH), (3)) with 2(diphenylphos-
phino)ethyl-triethoysilane [Ph2PCH2CH2Si(OCH2CH3)3] (dpts) and
tris(hydroxymethyl)phosphine [P(CH2OH)3] (thp) were also
the
alkynols
with
triethoxysilyl-propyl-isocyanate
(tsi)
[(H3CCH2O)3Si(CH2)3NCO] [6] and other alkoxysilyl-contaning li-
gands [7].
These ligands also, in some instances, undergo cleavage of the
(O=)C–O–NH bonds giving fragments which still coordinate to
metals using C@N bonds instead of the alkyne C„C bonds [8]. As
* Corresponding author.
E-mail address: sappa@unipmn.it (E. Sappa).
0022-328X/$ - see front matter Ó 2009 Elsevier B.V. All rights reserved.
doi:10.1016/j.jorganchem.2009.08.040

4242
F. Carniato et al. / Journal of Organometallic Chemistry 694 (2009) 4241–4249
examined. These ligands could ensure a stable grafting to silica-
based materials. With dpts mono- and di-substituted phosphinic
derivatives were obtained and were characterized by analytical
and spectroscopic techniques. In contrast thp did not give CO sub-
stitution. The structures of the complexes Co2(CO)6[Ph2PCH2CH2-
The FT-IR spectra were obtained on a Bruker Equinox 55 (KBr
cells, path length 0.5 mm) with pyroelectric DTGS detector (data
elaboration through Opus 5.0 software) and ATI-Mattson (data
elaboration software WinFIRST). The spectrum of Co/SBA-15 was
recorded under vacuum: the sample was pressed in the form of
self-supporting wafers and placed into a IR cell equipped with
KBr windows, permanently attached to a high vacuum line (resid-
ual pressure 1.0 ꢁ 10ꢀ6 Torr).
Si(OCH2CH3)3]2 (5) and of Co2(CO)4[l-g
2-(C„C(CH2OH)2)]
[Ph2PCH2CH2Si(OCH2CH3)3]2 (8) have been determined by X-ray
analyses. (5) has been grafted on the mesoporous SBA-15 [10]
and the material obtained has been characterized by inductively
coupled plasma-mass spectrometry (ICP-MS), infared spectroscopy
under vacuum conditions, X-ray diffraction (XRD), and scanning
electron microscopy coupled to EDS probe (SEM–EDS).
Thermogravimetric analyses were performed using a TA Instru-
ments SDT 2960 apparatus. The analyses were performed under a
N2 stream (10–100 cm3/min) using 10–15 mg samples and heating
at 10 °C/min from 25 to 800 °C, operating system TA 2000 Opera-
tive System.
The XRD analyses were performed on a Thermo ARL X’TRA 48
2. Experimental
instrument using the Cu Ka radiation (k = 1.54062 Å). Scanning
Electron Microscopy (SEM) analyses were performed using a LEO
1450 VP instrument. The surface of the solids was coated with a
thin gold layer to ensure surface conductivity. Energy Dispersive
X-ray spectroscopy (EDS) was used to provide rapid semiquantita-
tive elemental analyses on the sample surface.
2.1. General experimental details. Analysis of the products
2.1.1. Materials
Co2(CO)8 (Strem Chemicals), 3-pentyn-1-ol, 1,4-butyn-diol and
2-methyl-3-butyn-2-ol (Lancaster Syntheses) were commercial
products; tsi and teos were obtained from Sigma–Aldrich. The
phosphinic ligand dpts was from ABCR (Gelest, Karsruhe). All were
used as received. Solvents (e.g. hexane, heptane, diethyl ether and
toluene) were laboratory grade and were dehydrated over sodium.
Ethanol, HCl (37%) and NaF were laboratory grade reagents (Carlo
Erba). The reactions of (1) with tsi were performed following an al-
ready established procedure [6]. The reactions of (1) with teos and
those of (5) with SBA-15 are described below.
2.2. Reaction of Co2(CO)8 with pol, bud and mbo
2.2.1. Reaction with pol
Two grams (ca 7.0 mmol) of the cobalt carbonyl were sus-
pended in heptane under N2 and 3.0 cm3 of the alkyne (ca
12 mmol) were added. After reflux (7 + 8 min) the colour turned
deep-red. T.l.c. purification showed the presence of three bands,
blue, brown and brown (trace amounts, not investigated) and of
a red band (1) in 90% yields. Some decomposition was also
observed.
2.1.2. Synthesis of (1) and of the phosphine-substituted dicobalt
complexes
All the reactions were performed in heptane, under dry nitrogen
in conventional three-necked flasks, equipped with gas inlet, cool-
er, mercury check valve and magnetic stirring. The amounts of re-
agents are specified below. The yields of the products are
calculated on the reacted carbonyl. Reaction times reported indi-
cate the time required to bring the solution to reflux and the reflux
time (e.g. 6 + 7 min indicates 6 min to reflux followed by 7 min re-
flux). After reaction the suspensions were filtered under N2, re-
duced to small volume under vacuum and purified on t.l.c. plates
(Kieselgel P.F.Merck, eluants mixtures of petroleum ether and
diethyl ether in 9:1 v/v ratio).
2.2.1.1. Complex (1). Anal. Calc. (formula): C, 35.67; Co, 31.89; H,
2.16. Found: C, 35.5; Co, 31.9; H, 2.2%. IR (heptane): 2088 m,
2048 s, 2025 vs, 2016 s(sh), 2005 m(sh), 1974 w, cmꢀ1 1H NMR:
.
3.90 m (2H, CH2), 3.07 m (2H, CH2), 2.66 m (3H, CH3), 2.17 d (1H,
OH). Mass spectra (m/z): 370, M+; (mass numbers) [MꢀnCO]+
(n = 1–6).
2.2.2. Reaction with bud
The synthesis and molecular structure of complex (2) has been
previously reported [11]. An improved synthetic method has been
described [6].
2.1.3. Analysis of the organometallic complexes
2.2.3. Reaction with mbo
The IR spectra (solvent heptane) were obtained on a Brucker
Vector 22 (KBr cells, path length 0.5 mm). The 1H, 13C and the
29Si NMR spectra were registered on a JEOL Eclipse 400. Solvents
used were CDCl3 and CD3OD (for the complexes presumably con-
taining thp). The EI and CI mass spectra were obtained on a Finni-
gan-Mat TSQ-700 mass spectrometer (Servizio di spettrometria di
massa, Dipartimento di Scienza e Tecnologia del Farmaco, Univer-
sità di Torino). The ESI (positive and negative ions) mass spectra
were obtained on a Finnigan-Mat LCQ Duo spectrometer under
the following conditions: steath gas (necessary for the nebulisation
process) flow rate 80 (arb. units), aux. gas flow rate 0, spray voltage
4.50 kV, capillary temp. 270 K, capillary voltage 10 V, tube lens off-
set 0 V.
Two grams (ca 7.0 mmol) of the cobalt carbonyl were sus-
pended in heptane and 1.5 cm3 of the alkyne (ca 20 mmol) were
added. After reflux (8 + 8 min) the colour turned dark red. T.l.c.
showed the presence of only one orange-red band (3) in about
70% yields and some decomposition.
2.2.3.1. Complex (3). Anal. Calc. (formula): C, 35.67; H, 2.16; Co,
31.89. Found: C, 35.7; H, 2.2; Co, 32.0%. IR (heptane): 2096 m,
2055 vs, 2033 vs, 2025 s(sh), 2009 m(sh), cmꢀ1 1H NMR (CD3OD):
.
6.31 s (1H, HCꢂ), 3.59, 3.29 s (1H, OH), 1.64 m (3H, CH3), 1.54–1.06
m (3H, CH3). 13C NMR: 17.03 s (CH3), 30.4–32.5 t (CH3), 57.0 s
(C(OH)), 71.8 s (C„C), 145.2 t (HC„), 200.0 s (vb) (CO). Mass spec-
tra (m/z) = 370, M+.
2.1.4. Characterization of the sol–gel materials
2.3. Synthesis of the phosphine-substituted complexes
The chemical composition of the material obtained from SBA-15
(Co/SBA-15) was determined by inductively coupled plasma-mass
spectrometry (ICP-MS) [ITECON s.r.l., Nizza Monferrato, AT, Italy]
under the following conditions: alkaline fusion of the materials
with LiBO3 at 1100 °C for 30 min. Dissolution in ultrapure water
contaning about 2% of HNO3 followed by ICP-MS analysis.
2.3.1. Reaction of Co2(CO)8 with dpts
About 1.0 g [ca 3.5 mmol] of Co2(CO)8 was dissolved in heptane
under N2 and 1.0 cm3 [ca 3.0 mmol] of dpts was added. The milky
suspension was refluxed (7 + 7 min), after which time the colour
turned to dark brown. T.l.c. showed the presence of a dark brown

F. Carniato et al. / Journal of Organometallic Chemistry 694 (2009) 4241–4249
4243
band (40%, (4)), trace amounts of a blue complex (not collected)
and a red band (50%, (5)).
and the suspension refluxed again (4 + 8 min). T.l.c. yields (8) in
about 30% yields.
2.3.4.1. Complex (8). Anal. Calc. (formula): C, 53.38; H, 5.69; Co,
10.50; P, 5.52. Found: C, 53.4; H, 5.7; Co, 10.6; P, 5.50%. M.w. 1124.
IR (heptane): 2090 m, 2047 vs, 2018 vs, 1974 s, 1965 s(sh),
2.3.1.1. Complex (4). Anal. Calc. (formula): C, 46.96; H, 4.20; Co,
17.10; P, 4.49; 4.40. Found: C, 47.0; H, 4.3; Co, 17.2; P, 4.40%.
M.w. 690. IR (heptane): 2082 m, 2039 vs, 2027 m(sh), 2006 w,
cmꢀ1 1H NMR: (broad signals): 7.35 s (Ph), 3.70 s (CH2Et), 2.30 s
.
1850 m, 1831 m, cmꢀ1 1H NMR: 7.87–7.20 (broad), 6.70 s(b) [10
.
(CH2), 1.62 s (CH2 bud), 1.14 s (CH3), 0.53 s (OH). 13C NMR: 3.86
s, 18.25 s, 25.53 s, 58.59 s, 62.51 s (CH2OH), 85.98 s (C„C),
128.51–132.31 m, 136.11 t, 206.94 s (CO). 31P NMR: 35.2 s, 50.1
s. C.I. mass spectrum: 1088. ESI mass spectrum: 562 (M++).
H, Ph), 4.04–3.49 d(b) (6H, CH2, Et), 3.56 d (2H, CH2), 2.35 s(vb)
(2H, CH2), 0.88 s (9H, CH3). 13C NMR: 18.39 s (CH3), 30.92 s
(CH2), 128.51 s, 130.96 s (Ph), 206.98 d (CO). 31P NMR: 34.9 s,
43.8 s. C.I. mass spectrum: 689 m/z (medium intensity), 664
(highly intense, -C2H2), 647 (intense). ESI mass spectrum: 733
m/z (M+ + solvent (CH3OH)), doubly charged ion at 345 m/z.
2.4. Other reactions
2.4.1. Reaction of Co2(CO)6(pol) (1) with tsi
2.3.1.2. Complex (5). Anal. Calc. (formula): C, 53.18; H, 5.59; Co,
0.75 g (ca 2.0 mmol) of (1) were reacted with 2 cm3 (ca 8 mmol)
of tsi in heptane, under Ar for 5 min (up to reflux) and 10 min re-
flux. The t.l.c. plates showed the presence of a dark red band ((9),
ca 50%) and of decomposition (blue, 40%).
53.18; P, 5.97. Found: C, 53.2; H, 5.6; Co, 11.4; P, 6.0%. M.w. 1038.
IR (heptane): 1978 w, 1960 s, cmꢀ1 1H NMR: 7.70 s, 7.40 s (20
.
H, Ph), 4.20 s (12 H, CH2, Et), 2.50 s (4H, CH2), 1.20 s (18 H, CH3),
0.80 s (4H, CH2). 13C NMR: 17.2 d (CH3), 48.1 s (CH2), 57.0 s
(CH2), 128.7–131.8 mm (Ph), 198.0 (vb) (CO). 31P NMR: 59.6 s
(weak), 67.1 s (very intense). C.I. mass spectrum: 1002 m/z (low
intensity), 786 (intense), 740 (highly intense). ESI mass spectrum:
decomposition.
2.4.1.1. Complex (9). Co2(CO)6[H3CC„CCH2CH2OC(@O)NH(CH2)3-
Si(OEt)3]: Anal. Calc. (formula): C, 40.91; H, 4.38; Co, 29.22; Si,
4.54. Found: C, 41.0; H, 4.4; Co, 29.3; Si, 4.4%.
IR (heptane): 2090 m-s, 2050 vs, 2028 vs, 2019 s(sh), 2006
m(sh), 1725 s, 1699 m(b) cmꢀ1 1H NMR: 4.36 b (1H, NH), 3.80 d
.
2.3.2. Reaction of Co2(CO)6(pol) (1) with dpts
(2H, NCH2), 3.21 b (4H, „CCH2CH2), 2.64 s (4H, (CH2)2), 1.64 b
(6H, SiCH2), 1.20 s (9H, CH3), 0.62 s(b) (CH3C„). 13C NMR: 7.80
m, 18.34 s, 20.2–23.3 m, 32.3 s, 43.3 d, 45.5 m, 58.5 d, 66.3 s
(CH3, CH2), 92.0 s, 93.8 s (C„C), 149.0 s (C(@O)O), 154.1 s, 156.2
d, 199.6 b (CO). 29Si NMR: ꢀ42.22 vs. EI-MS: m/z 616 weak, release
of 6 CO and competitive complex fragmentation.
About 0.5 g [ca 1.4 mmol] of the cobalt complex were dissolved
in heptane under N2 and a small excess of dpts was added. The
solution was brought to reflux (6 + 6 min). T.l.c. showed the pres-
ence of a red band (80%, (6)) and of some decomposition.[12]
2.3.2.1. Complex (6). Anal. Calc. (formula): C, 53.74; H, 5.68; Co,
10.47; P, 5.68. Found: C, 53.7; H, 5.7; Co, 10.5; P, 5.7%. M.w. 1094.
IR (heptane): 2056 m, 2013 vs, 1967 (C vs(sh), 1958 vs, 1933 m-
2.5. Synthesis of the hybrid inorganic–organometallic materials
w(sh), cmꢀ1 1H NMR: 7.80 s, 7.50 s, 7.27 s (20H, Ph), 3.70 d (8H,
.
2.5.1. Reaction of Co2(CO)6(pol) (1) with teos
CH2), 2.40 d(b) (4H, CH2), 1.70 s (1 H, OH), 1.50 s(b) (12H, CH2,
Et), 1.10 d (18H, CH3, Et), 1.00–0.20 m (b) (3H, Me). 13C NMR
(CD3OD): 17.1 d, 22.2 s, 57.0 s, 58.4 s, 128.6–132.0 m (Ph), 200.0
(vb) (Co(CO)). 31P NMR: 49.3 s, 39.0 s. C.I. mass spectrum: 1058
m/z. ESI mass spectrum: decomposition.
A saturated heptane solution of (1) (10 cm3) was added to a sat-
urated solution of ethanol (10 cm3) containing 5 cm3 of teos: the
resulting solution was stirred and then evaporated under reduced
pressure. The solid obtained was dried under air (sample sga). An-
other attempt consisted in mixing the saturated heptane solution
of the complex with a saturated ethanolic solution of teos contain-
ing also 5 cm3 of H2O in which about 0.5 g of NaF had been dis-
solved. Gelation occurred more rapidly. The solution was stirred
and evaporated under reduced pressure, then dried in air. The
same material (sga) was obtained.
2.3.3. Reaction of Co2(CO)6(mbo) with dpts
About 1.0 g (ca 2.5 mmol) of (3) were dissolved in heptane–tol-
uene (50:50 vv: the complex is sparingly soluble in heptane) and
1.0 cm3 of dpts were added. After reflux (8 + 8 min), t.l.c. of the dark
red solution showed the presence of only one dark red band (7) in
about 90% yields.
2.5.2. Reactions of Co2(CO)6(dpts)2 with SBA-15
SBA-15 was treated under vacuum at 200 °C for 4 h in order to
remove the water and activate the surface. After cooling, a solution
of 50 mg of (5) in toluene was added. The suspension was then
warmed at 60 °C and stirred for 24 h. The final product was filtered,
washed several times with petroleum ether in order to dissolve
eventual soluble cobalt complexes and dried at room temperature
for 24 h.
2.3.3.1. Complex (7). Anal. Calc. (formula): C, 54.05; H, 5.94; Co,
10.67; P, 5.68. Found: C, 54.1; H, 5.9; Co, 10.7; P, 5.6%. M.w. 1110
IR (heptane): 2060 w, 2021 vs, 1967 vs, 1941 w, 1765 m, 1712
m, cmꢀ1. 1H NMR (very broad signals): 7.43 s, 3.76 s, 2.31 s, 1.18 s.
13C NMR (CD3OD): 1.29 s, 18.33 s, 23.0 d, 33.84 s, 58.65 s (C„C),
127.52–132.19 m, 196.0 (vb) (CO). 31P NMR: 35.3 s. C.I. mass spec-
trum: 1074. ESI mass spectrum: 555 (M++).
2.6. Crystallography
2.3.4. Reaction of Co2(CO)6(bud) with dpts
About 1.0 g [2.8 mmol ca] of the cobalt complex (2) and 1.0 cm3
[2.6 mmol ca] of dpts were dissolved in heptane under N2: a milky
suspension was obtained. This was refluxed (7 + 7 min). T.l.c. puri-
fication showed the presence of a dark brown band (40%, (8)), a
blue band (tr., not investigated) and a red band (50%, parent
complex).
Crystal and refinement data of (1), (5) and (8) are collected in
Table 1.
2.6.1. Complex (1)
Crystals were obtained from a n-heptane solution. The reflec-
tion data have been collected on
a Siemens P4 diffrac-
A”direct” synthetic pathway is the following. Reaction of
Co2(CO)8 with bud as previously described [6]. After reflux
(8 + 10 min) the solution is cooled, a slight excess of dpts is added
tometer equipped with a Bruker APEX CCD detector. The intensities
have been corrected semi-empirically for absorption, based on
symmetry equivalent reflections. The refinement was made using

4244
F. Carniato et al. / Journal of Organometallic Chemistry 694 (2009) 4241–4249
Table 1
Crystal data and structure refinement details.a
Complex
Co2(CO)6[
l
-
g
2-(H3CC„CCH2CH2OH)] (1)
Co2(CO)6[Ph2PCH2CH2Si(OCH2CH3)3]2 (5)
Co2(CO)4[
[Ph2PCH2CH2Si(OCH2CH3)3]2 (8)
l-g
2-(C„C(CH2OH)2)]
Formula
M
Crystal system
C
11H8Co2O7
C
46H70Co2O12P2Si2
C48H62Co2O12P2Si2
370.04
Monoclinic
P21/n
19.3349(18)
1051.00
Orthorhombic
Pbca
1067.00
Monoclinic
P21/n
Space group
0
14.3776(3)
15.396(3)
a (AÅ)
0
7.1829(6)
17.1866(4)
14.657(3)
b (AÅ)
0
20.7491(19)
22.2259(7)
25.467(3)
c (AÅ)
a
b (°)
c
(°)
90.
84.031(2)
90.
90.
90.
90.
90.
90.
90.
(°)
0
2831.0(4)
5492.1(2)
5478.1(17)
U (AÅ3)
Z
8
4
4
Crystal colour
Light yellow
Red
Red
Crystal dimensions (mm)
l
0.06 ꢁ 0.10 ꢁ 0.28
0.04 ꢁ 0.16 ꢁ 0.24
0.03 ꢁ 0.09 ꢁ 0.13
(Mo Ka )
) (mmꢀ1
2.368
0.76
0.76
Temperature (K)
120
293
293
h Range
1.32–25.00
3.00–32.79
2.88–29.43
Total no. reflections
Unique reflections
Rint
26882
4981
0.037
67815
9601
0.10
60339
13658
0.15
No. of parameters
364
241
327
b
R1 [I0 > 2
r(I0)]
0.0436[4385 obs.]
0.123
0.065[1944 obs.]
0.325
0.0724[2496 obs.]
0.359
R1 (all data)
wR2b[I0 > 2
r
(I0)]
0.165
0.200
0.79
0.165
0.213
0.76
wR2 (all data)
Goodness-of-fitc
1.054
a
b
c
Common items: wavelength (Mo Ka) = 0.71073 Å.
R .
w(F2o )2]
½
R1
=
R
||Fo|ꢀ|Fc||/
R
|Fo|, wR2 = [
R
(wFo2ꢀFc2)2/
G.O.F. (Goodness Of Fitness) =
R
(wF2o ꢀFc2)2/(no.of unique reflections – no. of parameters).
full-matrix least-squares on F2. The asymmetric unit contains two
molecules. All non-hydrogen atoms were refined anisotropically.
The hydrogen atoms have been located and then kept fixed with
Uiso set at 1.2 times Ueq of the corresponding C atom and 1.5 Ueq
of the corresponding O atom.
Programs used were SHELXTL [13] for structure solution, refine-
ment and molecular graphics, BRUKER AXS SMART (diffractometer con-
trol), SAINT (integration), SADABS (absorption correction)] [14]. The
CIF file is deposited at CSD as CCDC 714073.
groups and those linked to the ethoxy groups, have been calculated
and then kept riding with Uiso set at 1.2 times Ueq of the corre-
sponding C atom. All other atoms have been refined anisotropically
with the exclusion of atoms of the ethoxy groups, that have been
refined isotropically with restraints. The phenyl groups were also
refined with the constrained exact hexagonal geometry. This
refinement strategy has been considered suitable owing to the very
high thermal motion of the atoms and to the poor quality of all
crystals measured.
Programs used were CRYSALISPRO [15] for data collection and cor-
rection and SHELXTL [13] for structure solution, refinement and
molecular graphics. The CIF file is deposited at CSD as CCDC 738899.
2.6.2. Complex (5)
The reflection data, using a crystal obtained from a heptane
solution, have been collected on a Gemini R Ultra diffractometer
[15]. The refinement was made using full-matrix least-squares on
F2. The hydrogen atoms, with the exclusion of those linked to the
ethoxy groups, have been calculated and then kept riding with Uiso
set at 1.2 times Ueq of the corresponding C atom. All other atoms
have been refined anisotropically with the exclusion of atoms of
ethoxy groups, that have been refined isotropically with restraints.
This refinement strategy has been considered suitable owing to the
very high thermal motion of the atoms.
3. Results and discussion
The reactions performed during this work and leading to phos-
phine-substituted complexes and to inorganic–organometallic
materials are summarized in Scheme 1.
3.1. Synthesis of the complexes Co2(CO)6(pol) and Co2(CO)6(mbo)
Programs used were CRYSALISPRO [15] for data collection and cor-
rection and SHELXTL [13] for structure solution, refinement and
molecular graphics. The CIF file is deposited at CSD as CCDC
738898.
The reaction of Co2(CO)8 with pol gives high yields of the ex-
pected complex Co2(CO)6(H3CC„CCH2CH2OH) (1) which shows
the well known ‘‘pseudo-tetrahedral” structure first reported for
Co2(CO)6(PhC„CPh) [16,17].
The reaction of Co2(CO)8 with bud and the structure of the
resulting (2) have already been reported [11,6]. The reaction of
the cobalt carbonyl with mbo gives Co2(CO)6(HC„C(CH3)2OH),
(3) in high yields. Elemental analyses and spectroscopic evidence
indicate that (3) contains an intact ligand and that no dehydration
has occurred during the synthesis.
2.6.3. Complex (8)
The reflection data, using a crystal obtained from a heptane
solution, have been collected on a Gemini R Ultra diffractometer
[15]. The refinement was made using full-matrix least-squares on
F2. The hydrogen atoms, with the exclusion of those of the OH

F. Carniato et al. / Journal of Organometallic Chemistry 694 (2009) 4241–4249
4245
EtO
OEt
HO
OEt
OEt
EtO
EtO
Si
CH
2
Si
H
C
2
OC
CO
Co
CO
C
C
dpts
H
C
2
H2
HO
C
P
Co
P
H
2
CH2
Ph
Ph
OC
C
Ph
Ph
OC
OC
OC
C
CO
CO
decomposition
thp
H C
2
no reaction
Co
Co
OH
CO
C
thp
no reaction
H2C
thp
CH3
EtO
EtO
EtO
OEt
bud
OH
OC
O
Si(OCH2CH3)4
O
C
C
CO
CO
OEt
OEt
C
C
sga
Si
Si
CH
OC
OC Co
OC
CO
3
pol
Co
CO
H
2
OC
OC
Co
Co CO
C
OC
C
CO
Co
C
H2
Co2(CO)8
H
C
Ph
CH2
CH2
Si
dpts
2
P
C
Ph
P
Co
P
H
2
dpts
mbo
CH2
OH
OEt
OEt
CO
Ph
Ph
OC
C
tsi
Ph
EtO
H
Ph
CH
H2C
CO
CO
CO
2
OC
OC
OC
C
H C
2
Co
Co
CO
Co
OH
CO
C
O
C
O
C
OC
C
C
CH3
CH3
OC
OC
OCH2CH3
CO
O
C
H
N
C
H2
C
H2
OCH2CH3
OCH2CH3
Si
O
C
H3C
dpts
Co
CO
Co
C
C
C
HO
H2
H2
H2
Ph
P
Ph
P
Co
Ph
H
2C
C
H2
OC
CO
Ph
OC
EtO
EtO
EtO
CH2
OEt
C
H2
OEt
OEt
Si
OEt
Si
H
H
C
2
Si
OC
OC
Si
C
CO
Co
C
H2
H
C
2
EtO
C
P
Co
P
H
2
OEt
OEt
EtO
CO
Ph
Ph
C
OEt
Ph
CH
SBA-15
3
Ph
C
CH
3
HO
Co/SBA-15
Scheme 1.
3.2. The reactivity of Co2(CO)6(pol)
1.33(3)–1.36(1) Å [16]. In the latter compounds the Co–Co and
the CoꢃꢃꢃC(alkyne) distances are in the ranges 2.460(1)–2.477(3)
and 1.92(2)–1.987(2) Å, respectively.
By exploiting the reactivity of the cobalt-coordinated pol it was
possible to build a new coordinated ligand [7]. Indeed (1) reacts
with tsi to give good yields of the new complex Co2(CO)6
[H3CC„CCH2CH2OC(@O)NH(CH2)3Si(OEt)3] (9) which has been
characterized by spectroscopic analyses. Previous experience [6]
indicates that this type of complexes can be easily grafted on teos
and/or undergo oligomerization; this is presumably the reason
why we could not obtain crystals suitable for a X-ray analysis.
For (9) the well known structure with C„C perpendicular to the
3.4. Reactions of Co2(CO)8 and of (1),(2), (3) with the phosphinic
ligands
3.4.1. Reactions of Co2(CO)8 with dpts
The reaction of the cobalt carbonyl with dpts yields two prod-
ucts, (4) and (5). In spite of many attempts (by changing solvent
and conditions) crystals of (4) suitable for X-ray analysis could
not be obtained. The IR spectra indicate the presence of two bridg-
ing carbonyls and the NMR data and the CI and ESI mass spectra
Co–Co bond can be proposed, with formula Co2(CO)6[[l- -
g2
(CH3C„C(CH2CH2)2 OC(@O)NH(CH2)2Si(OEt)3].
exclude the possibility that (4) is a Co4(CO)8(
[18] or a Co3(CO)7( -CO)2( 3-L) methylidyne complex [19]. The
proposed structure is therefore Co2( -CO)2(CO)5(dpts) and is
l-CO)2(L) butterfly
3.3. The molecular structure of Co2(CO)6[l-g
2-(H3CC„CCH2CH2OH)]
(1)
l
l
l
shown in the Fig. 2 (below): it is known that the parent compound
Co2(CO)8 in the solid-state has a structure with two bridging car-
bonyls [20]. To our knowledge in the literature a phosphine-mon-
osubstituted dicobalt complex has been reported with only
terminal CO groups [21] and a trisubstituted complex with formula
Co2(l-CO)2(CO)3[P(CH3)2Ph]3 [22] is known.
In contrast, the reaction of the cobalt carbonyl with thp resulted
only in decomposition. No soluble products could be isolated.
The structure of (1) is shown in the Fig. 1 and relevant distances
and angles are listed in Table 2 for both molecules.
The complex (Fig. 1 and Table 2) contains a pseudo-tetrahedral
arrangement of two cobalt atoms and two carbon atoms of the
elongated C„C bond of the alkyne (Co(1)–Co(2) 2.4690(9) Å av.,
C(2)–C(3) 1.326(6) Å av.). Three terminal carbonyl groups are
bound to each cobalt atom. The elongated triple bond is perpendic-
ular to the Co–Co bond according to a well known geometry
(CoꢃꢃꢃC(alkyne) 1.972(4) Å av.). The X-ray analysis shows that no
loss of the alkyne functionality has occurred.
3.4.2. Reactions of Co2(CO)6(pol) with dpts
Complex (1), whose structure is described above, has been re-
acted with dpts. Very high yields (90%) of the unique (6) could be
obtained. Unfortunately no crystals suitable for X-ray analyses
The C(2)–C(3) distance is well comparable with those in
Co2(CO)6(C2R2) with R = Ph, CO2Me,But, lying in the range

4246
F. Carniato et al. / Journal of Organometallic Chemistry 694 (2009) 4241–4249
also, is a disubstituted product. The proposed structure is analo-
gous to that of (8).
3.4.4. Reactions of Co2(CO)6(bud) with dpts
The cobalt complex (2) whose structure had already been re-
ported [11], has been reacted with dpts: one complex only, (8),
was obtained in high yields.
3.4.5. Reactions of Co2(CO)6(pol) and of Co2(CO)6(bud) with thp
As already shown for Co2(CO)8, also from these reactions no
phosphine-substituted complexes could be obtained. Only some
decomposition products were found. This is probably due to the
low electron donor power of the phosphine (low
r Taft). Therefore
thp is not suitable for grafting cobalt carbonyls on inorganic
substrates.
3.5. The molecular structures of the phosphine-substituted complexes
3.5.1. The molecular structure of Co2(CO)6(dpts)2
The structure of the complex is shown in Fig. 3 and relevant dis-
tances and angles are in Table 3. The molecule lies on a crystallo-
graphic inversion centre, therefore all substituents on Co atoms
are in a staggered or anti configuration.
Fig. 1. ORTEP plot (50%) of one molecule of Co2(CO)6[l-g
2-(H3CC„CCH2CH2OH)]
complex with atom labelling.
The comparison with the parent compound Co2(l-CO)2(CO)6
Table 2
[20] shows that the double substitution results in the ‘‘loss” of
the bridging carbonyls and in the elongation of the Co–Co bond
distance (2.661(1) Å versus 2.526(1) Å). A number of disubstituted
complexes with phosphinic terminal ligands shows the range of
the Co–Co bond distances around 2.66 Å. Selected examples are
the Co2(CO)6L2 derivatives where L = PPh3 [23], P(OPh)3 [24],
P(CH3)3 [25], PPh2(CH2P(@O)Ph2)3 [26a,b], PPh2(C6H4N(CH3)2)
[27], P(CH3)2Ph [22], PPh2(CH2C(@O)Ph) [28], P(OPri)3 [29].
Relevant bond lengths (Å) and angles (°) for the two independent molecules.
Co(1)–Co(2)
Co(1)–C(11)
Co(1)–C(12)
Co(1)–C(13)
Co(1)–C(2)
Co(1)–C(3)
Co(2)–C(21)
Co(2)–C(22)
Co(2)–C(23)
Co(2)–C(2)
Co(2)–C(3)
C(1)–C(2)
C(2)–C(3)
C(3)–C(4)
C(4)–C(5)
C(5)–O(6)
C(3)–C(2)–C(1)
C(2)–C(3)–C(4)
C(3)–C(4)–C(5)
O(6)–C(5)–C(4)
2.4722(9)
1.784(5)
1.823(5)
1.817(5)
1.969(4)
1.974(4)
1.790(5)
1.825(5)
1.815(5)
1.969(4)
1.966(4)
1.489(6)
1.334(6)
1.484(6)
1.514(6)
1.430(5)
143.9(4)
142.0(4)
113.1(4)
113.0(4)
2.4658(8)
1.796(5)
1.835(5)
1.824(5)
1.955(4)
1.974(4)
1.779(5)
1.811(5)
1.828(5)
1.983(4)
1.963(4)
1.494(6)
1.319(6)
1.501(6)
1.529(6)
1.419(6)
144.8(4)
143.2(4)
111.6(4)
112.2(4)
3.5.2. The molecular structure of Co2(CO)4(bud)(dpts)2 (8)
It belongs to the well known carbonyl complexes bearing an
acetylenic moiety perpendicularly
p-bonded to a Co–Co bond
and six terminal ligands. Every Co atom links two CO groups and
a phosphine ligand. The structure of (8) is shown in Fig. 4 and rel-
evant distances and angles are in Table 3.
The four terminal CO ligands are eclipsed and the Co–Co bond
distance (2.472 Å) well compares with other similar complexes
O
O
C
C
OC
OC Co
OC
CO
Co CO
Ph
CH2
CH2
Si
P
Ph
OEt
OEt
EtO
Fig. 2. Proposed structure of (4), Co2(CO)7(dpts).
could be obtained. Spectroscopic results indicate that this could be
the disubstituted Co2(CO)4(pol)(dpts)2. The proposed structure is
analogous to that of (8).
3.4.3. Reaction of complex Co2(CO)6(mbo) with dpts
Complex (3) reacts with dpts giving, as the unique product, (7)
in good yields. Spectroscopic evidence indicates that this complex,
Fig. 3. ORTEP view (30% probability) of (5) Co2(CO)6[Ph2PCH2CH2Si(OCH2CH3)3]2,
with atom labelling. Atoms with label
inversion centre.
A are related by the crystallographic

F. Carniato et al. / Journal of Organometallic Chemistry 694 (2009) 4241–4249
4247
Table 3
Relevant bond lengths (Å) and angles (°) for (5) and (8).
(5)
Co(1)–Co(1A)
Co(1)–C(1)
Co(1)–C(2)
Co(1)–C(3)
Co(1)–P(1)
P(1)–C(16)
C(16)–C(17)
C(17)–Si(2)
C(3)–Co(1)–C(2)
C(3)–Co(1)–C(1)
C(2)–Co(1)–C(1)
C(3)–Co(1)–Co(1A)
C(2)–Co(1)–Co(1A)
C(1)–Co(1)–Co(1A)
P(1)–Co(1)–Co(1A)
Co(1)–Co(2)
Co(1)–C(11)
Co(1)–C(12)
Co(1)–C(3)
Co(1)–C(2)
Co(1)–P(1)
Co(2)–C(21)
Co(2)–C(22)
Co(2)–C(3)
Co(2)–C(2)
Co(2)–P(2)
C(1)–O(1)
C(1)–C(2)
C(2)–C(3)
C(3)–C(4)
C(4)–O(2)
P(2)–Co(2)–Co(1)
P(1)–Co(1)–Co(2)
O(1)–C(1)–C(2)
C(3)–C(2)–C(1)
C(2)–C(3)–C(4)
O(2)–C(4)–C(3)
2.6611(11)
1.774(7)
1.779(6)
1.738(7)
2.1904(12)
1.819(5)
1.527(6)
1.852(5)
120.8(3)
121.3(3)
116.4(2)
80.84(15)
87.47(15)
89.78(16)
172.31(6)
2.4725(14)
1.762(9)
1.772(11)
1.960(7)
1.970(8)
2.207(2)
1.789(9)
1.798(10)
1.942(7)
1.983(8)
2.219(2)
1.391(9)
1.497(10)
1.312(9)
1.543(10)
1.407(9)
153.86(8)
151.86(8)
110.2(7)
140.9(7)
137.3(8)
108.2(7)
(8)
Fig. 5. ORTEP plot (30% probability) showing the geometry of the alkyne ligand and
the eclipsed configuration of the CO groups in (8).
3.6. The synthesis and characterization of hybrid materials
3.6.1. Reaction of (1) with tsi
The reactivity of (1) can be exploited for grafting directly the
complex to teos. We could obtain, indeed, a new inorganic–organo-
metallic material (sga) which has been characterized by spectro-
scopic techniques. The material sga is a very fine amorphous
powder (as shown by a XRD analysis) with a relatively low surface
area of 150 m2/g and a very irregular distribution of the pore
dimensions. Unfortunately the Raman spectrum showed the fluo-
rescence typical of the presence of metal centres. The IR (KBr pel-
lets) showed the following signals: 3500–3100 vb, 2900 b (ligand
CH3, CH2, surface OH), 2095, 2054, 2027 (mCO), 1710 (O–C), 1553
(O–Si), 1250–900 (skeletal vibration of SiO2) [30]. The TGA analysis
showed losses of weight between 50 and 100 °C (loss of residual
solvent) and at 280 °C (loss of CO and organic fragments).
3.6.2. Reactions of (5) with SBA-15
Due to the presence of two triethoxy groups, (5) was success-
fully anchored on the surface silanols of SBA-15 mesoporous sup-
port. The chemical analysis performed by ICP-MS showed that
the final hybrid material based on SBA-15 (Co/SBA-15), contains
22.7 and 0.6 mg/g of Co and P, respectively.
Particular attention was devoted to the investigation of the
morphological and structural properties of the mesoporous silica
after reaction with (5). The morphology of the pristine SBA-15, de-
tected by scanning electron microscopy, was not modified upon
anchoring. Co/SBA-15 preserved, in fact, a rod-like morphology
with particle dimensions around 1 lm, typical of the pristine sup-
port (Fig. 6). In addition, EDS analysis highlighted an homogeneous
distribution of cobalt in the final material according to the ICP-MS
analysis.[31]
X-ray diffraction pattern of pristine SBA-15 (Fig. 6B, curve a)
shows three distinct reflections: one intense peak at 0.87° 2h and
two weak reflections at 1.5 and 1.7 2h, which can be indexed as
the (1 0 0), (1 1 0) and (2 0 0) planes related to the hexagonal pore
arrray of SBA-15.[10] This pattern was also preserved after anchor-
ing. However, Co/SBA-15 showed a decrease of the peak intensities,
along with a shift to higher 2h, which is assigned to the immobili-
zation of cobalt cluster inside the SBA-15 pores (Fig. 6B, curve b).
Particular attention was also devoted to the investigation of the
vibrational profiles of the porous material before and after reaction
with the cobalt complex. The Infrared spectrum of Co/SBA-15 re-
corded under vacuum conditions, was compared with that of the
pristine support (Fig. 7). The spectrum of SBA-15 (Fig. 7, solid lines)
in the range 4000–3000 cmꢀ1 showed two different signals. The
peak at 3745 cmꢀ1 is due to the stretching of isolated silanol
Fig.
4. ORTEP
plot
(30%
probability)
of
(8),
Co2(CO)4[l- -
g2
(C„C(CH2OH)2)][Ph2PCH2CH2Si(OCH2CH3)3]2, with atom labelling.
(see (1)). The two phosphinic ligands are cis with respect to the
Co–Co bond. The 1,4-butyn-diol, HOCH2C„CCH2OH, with the elon-
gation of the C„C bond, assumes the structure of an alkene with
the CH2OH substituents related by a non crystallographic mirror
plane defined by the Co(1)Co(2) atoms and by the middle point
of the C(2)–C(3) bond (Fig. 5).

4248
F. Carniato et al. / Journal of Organometallic Chemistry 694 (2009) 4241–4249
Fig. 6. SEM micrograph at lower (A) and higher magnification (A0) of Co/SBA-15. X-ray profiles of SBA-15 (a) and Co/SBA-15 (b) are reported in B.
Starting from cobalt centres with coordinated alkynols it is pos-
sible to obtain new functionalized complexes: these are mono- and
disubstituted phosphine complexes with structures predictable on
the basis of literature reports (even if, in some instances, the dispo-
sition of the ligands were not predictable with certainty). The
derivatives containing dpts are suitable for grafting to sol–gel silica
containing materials using the triethoxysilyl functionalities. This
behaviour had already been observed for ruthenium carbonyl clus-
ters [9]. In the case of cobalt, however, after grafting the unmodi-
fied cluster was found.
The above results show that the synthetic approach followed in
this work may lead to a wide variety of inorganic–organometallic
materials useful for catalysis and other applications.
References
[1] (a) R.J.P. Corriu, D. Leclerq, Angew. Chem., Int. Ed. 35 (1996) 1420–1436;
Fig. 7. IR spectra under vacuum conditions of SBA-15 (solid line) and Co/SBA-15
(short dashed line).
(b) U. Schubert, J. Chem. Soc., Dalton Trans. (1996) 3343–3348.
[2] (a) A. Choualeb, J. Rosé, P. Braunstein, R. Welter, Organometallics 22 (2003)
2688–2693;
(b) A. Choualeb, P. Braunstein, J. Rosé, S.E. Bouaud, R. Welter, Organometallics
22 (2003) 4405–4417;
(c) A. Choualeb, P. Braunstein, J. Rosé, R. Welter, Inorg. Chem. 43 (2004) 57–71.
[3] G. Gervasio, D. Marabello, E. Sappa, A. Secco, J. Organomet. Chem. 690 (2005)
3730–3736.
groups (Si–OH). The broad band in the 3700–3200 cmꢀ1 range is
assigned to Si–OH involved in hydrogen bonds. After reaction with
(5), (Fig. 7, short dashed lines), the intensity of the isolated silanols
drastically decreased and the shape of the broad band al lower
wavenumber (around 3500 cmꢀ1) was modified.
[4] (a) G. Gervasio, D. Marabello, E. Sappa, A. Secco, J. Organomet. Chem. 690
(2005) 3755–3764;
(b) G. Gervasio, D. Marabello, E. Sappa, A. Secco, Can. J. Chem. 84 (2006) 337–
344.
These results suggested that a significant fraction of silanols of
SBA-15 were involved during the grafting reaction with (5).
In addition, the typical absorptions of (5) (bands at 3060 and
[5] (a) G. Gervasio, D. Marabello, P.J. King, E. Sappa, A. Secco, J. Organomet. Chem.
671 (2003) 137–144;
(b) G. Gervasio, D. Marabello, P.J. King, E. Sappa, A. Secco, J. Organomet. Chem.
689 (2004) 35–42;
(c) G. Gervasio, D. Marabello, E. Sappa, A. Secco, J. Organomet. Chem. 690
(2005) 1594–1599.
1955 cmꢀ1, assigned to the
m(C–H) of phenyl groups and m(CO),
respectively) were found in the vibrational profile of Co/SBA-15,
confirming that the complex structure was preserved during the
anchoring procedure.
[6] A. Arrais, E. Boccaleri, E. Sappa, A. Secco, J. Sol–Gel Sci. Technol. 38 (2006) 283–
292.
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The results obtained indicate that starting from Co2(CO)8 and
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