Reaction of ruthenium phenyl acetylide with iron-chalcogen clusters and iron pentacarbonyl

Article abstract of DOI:10.1016/j.jorganchem.2013.02.001

Photolysis of a THF solution containing ruthenium acetylide [(η⁵-C₅H₅)Ru(PPh₃) ₂(η¹-CCPh)] with [Fe₃(CO) ₉(μ₃-Se)₂] cluster affords an adduct [{μ-SeC(CpRu(PPh₃)(CO))C(Ph)Se}(CO)₆Fe₂] (1), while under similar reaction condition with [Fe₃(CO) ₉(μ₃-Te)₂] cluster a Ru-inserted product [(η⁵-C₅H₅)(PPh₃) (η¹-CCPh)RuFe₂(μ₃-Te) ₂(CO)₆] (2) was obtained. Under thermal condition [(η⁵-C₅H₅)Ru(PPh₃) ₂(η¹-CCPh)] react with Fe(CO)₅ to give an acetylide stabilised Fe₂Ru mixed metal cluster [(η⁵- C₅H₅)RuFe₂(CO)₇(η²: η²:η¹-CCPh)], (3).

Full text of DOI:10.1016/j.jorganchem.2013.02.001

Journal of Organometallic Chemistry 731 (2013) 55e60
Contents lists available at SciVerse ScienceDirect
Journal of Organometallic Chemistry
journal homepage: www.elsevier.com/locate/jorganchem
Reaction of ruthenium phenyl acetylide with iron-chalcogen clusters and iron
pentacarbonyl
,
b
,
a
a
b,c
Pradeep Mathur a , Abhinav Raghuvanshi , Radhe Shyam Ji , Shaikh M. Mobin
*
a Department of Chemistry, Indian Institute of Technology Bombay, Powai, Mumbai 400076, India
b School of Sciences, Indian Institute of Technology Indore, Khandwa Road, Indore 452017, India
c Sophisticated Instrumentation Centre, Indian Institute of Technology Indore, Khandwa Road, Indore 452017, India
a r t i c l e i n f o
a b s t r a c t
Photolysis of a THF solution containing ruthenium acetylide [(h h
5-C5H5)Ru(PPh3)2( 1-C^CPh)] with
Article history:
Received 5 November 2012
Received in revised form
1 February 2013
[Fe3(CO)9(m3-Se)2] cluster affords an adduct [{
under similar reaction condition with [Fe3(CO)9(m3-Te)2] cluster
C5H5)(PPh3)(
1-C^CPh)RuFe2(m3-Te)2(CO)6] (2) was obtained. Under thermal condition [(
Ru(PPh3)2(
1-C^CPh)] react with Fe(CO)5 to give an acetylide stabilised Fe2Ru mixed metal cluster [(h5
C5H5)RuFe2(CO)7(h2 h2 1-C]CPh)], (3).
m-SeC(CpRu(PPh3)(CO))]C(Ph)Se}(CO)6Fe2] (1), while
a
Ru-inserted product [(h5
-
h
h
5-C5H5)
Accepted 4 February 2013
h
-
:
:h
Keywords:
Ruthenium acetylide
Photolysis
Ó 2013 Elsevier B.V. All rights reserved.
Adduct
Mixed metal cluster
1. Introduction
are bridged head-to-head by a [Fe(CO)2] unit [17e19]. Further, in
some clusters the acetylide units remained uncoupled [20].
More variations are also expected by using different types of
metal acetylides with chalcogen-bridged metal carbonyl com-
pounds and different metal carbonyls. In this paper, we report on
our investigation on reactions of a non-carbonyl metal acetylide
Chemistry of metal acetylide complexes continues to attract
attention for the construction of organometallic polymers [1e7]
and as components in non-linear optical materials [8e10]. Mono-
nuclear acetylide complexes are versatile building blocks in cluster
growth reactions and a number of polycarbon ligand-containing
metal clusters have been prepared from mononuclear metal ace-
tylides [11e16]. As part of our studies on chalcogen-bridged clus-
ters, we have observed that when chalcogen-bridged metal
carbonyl compounds are used as precursors to react with metal
acetylide molecules, an equally rich and diverse set of acetylide-
incorporated mixed-metal clusters form, where the nature of
metal acetylide additions and acetylide coupling are strongly
dependent on the nature of chalcogen used, the metal atom present
and also the reaction conditions [17e20]. Previously, we have re-
[(
h
5-C5H5)Ru(PPh3)2(
h
1-C^CPh)] with [Fe3(CO)9(m3-E)2] (E ¼ Se or
Te)] and with iron pentacarbonyl. Motivation for this study was to
obtain a new strategy for the formation of mixed metal and mixed
metal-chalcogen clusters.
2. Results and discussion
2.1. Reaction of [(h h
5-C5H5)Ru(PPh3)2( 1-C^CPh)] with
[Fe3(CO)9(m3-E)2]
ported the reactivity of mononuclear acetylide complexes [(h5
-
When
C^CPh)] and [Fe3(CO)9(m3-Se)2] was photolysed under continuous
bubbling of nitrogen at 0 ꢀC for 30 min, a formal adduct, of [(h5
C5H5)Ru(PPh3)(CO)(C^CPh)] and [Fe2(CO)6( -Se2)], [{ -SeC(C-
pRu(PPh3)(CO))]C(Ph)Se}(CO)6Fe2] (1) was obtained, along with
a THF solution containing [(h -
5-C5H5)Ru(PPh3)2(h1
C5H5)M(CO)3(
h
1-C^CPh)] (M ¼ Mo or W) with [Fe3(CO)9(m3-E)2]
(E ¼ S, Se, Te), where formation of a number of different Fe3M2E2 or
Fe4M2E2 type clusters was observed, having head-to-head, head-to-
tail and tail-to-tail coupling of two multi-coordinated acetylide
units, and also the ones which contain two acetylide groups which
-
m
m
the known compounds [Fe3(CO)8PPh3(m3-Se)2], [Fe2(CO)5PPh3(m-
Se)2] and SePPh3 (Scheme 1).
In contrast, when
Ru(PPh3)2(
1-C^CPh)] and [Fe3(CO)9(m3-Te)2] was photolysed at
ꢀC for 30 min, under nitrogen atmosphere, formation of a new
a THF solution containing [(h
5-C5H5)
* Corresponding author. School of Sciences, Indian Institute of Technology Indore,
Khandwa Road, Indore 452017, India. Tel.: þ91 7312368282.
h
E-mail addresses: mathur@iitb.ac.in, mathur@chem.iitb.ac.in (P. Mathur).
0
0022-328X/$ e see front matter Ó 2013 Elsevier B.V. All rights reserved.
http://dx.doi.org/10.1016/j.jorganchem.2013.02.001

56
P. Mathur et al. / Journal of Organometallic Chemistry 731 (2013) 55e60
pattern typically observed in the spectra of compounds containing
the [Fe2(CO)6] group. 1H NMR spectra of 1 and 2 confirm the
presence of phenyl and cyclopentadienyl groups.
The yields of 1 and 2 are rather low surprisingly, because even
under mild conditions and even in presence of stabilising bridging
chalcogen ligands we get a large amount of triphenylphosphine
substituted clusters [Fe3(CO)8PPh3(m3-E)2], [Fe2(CO)5PPh3(m2-E2)]
(E ¼ Se and Te) and [SePPh3], which indicates some amount of
cluster degradation. It is envisaged that in both the reactions, under
photolytic condition, a reactive coordinatively unsaturated species,
[(h h
5-C5H5)Ru(PPh3)( 1-C^CPh)] is initially formed, which in the
case of the reaction with [Fe3(CO)9(m3-Se)2] adds a CO and then
forms the adduct 1, whereas in the case of reaction with
[Fe3(CO)9(m3-Te)2], adds directly to form the adduct 2. We have not
found the formation of complex type 2 with Se-cluster and for-
mation of complex type 1 with Te-cluster. Also, isomerisation of 1
and 2 was not observed on heating.
The molecular structure of 1, shown in Fig. 1, consists of a but-
terfly [Fe2(CO)6Se2] unit and [CpRu{PPh3(CO)}C]CPh] unit added
across the open butterfly edge. Structure of 1 is similar to numerous
adducts obtained from the reaction of terminal acetylenes with
[Fe2(CO)6(
m
-E2)] complexes (E ¼ S, Se and Te) [21e23]. However,
this is the first example of a formal adduct formation with an in-
ternal acetylene. In compound 1, one of the PPh3 ligands on the
ruthenium is substituted by a CO ligand, probably due to the steric
interactions between the two PPh3 ligands.
Scheme 1. Photolysis of [(h h
5-C5H5)Ru(PPh3)2( 1-C^CPh)] with [Fe3(CO)9(m3-E)2].
Overall, the structure of 1 is similar to [{
E}(CO)6Fe2] (E [24], Se [25], Te [26]), [{
Te}(CO)6Fe2] [25], [{ -TeC(H)]C(Ph)Te}(CO)6Fe2] [21], [{
C(2-Th)Se}(CO)6Fe2] [23], and [{ -SC(C^CCH3)]C(H)Te}-(CO)6Fe2]
[24]. The CeC bond distance of 1.328(6) A indicates the reduction of
the acetylenic triple bond to an olefinic bond and is similar to cor-
m
m
-SeC(H)]C(Ph)
-SC(H)]C(Ph)
-SeC(H)]
ruthenium inserted mixed metal cluster [(
C^CPh) RuFe2(m3-Te)2(CO)6], (2) was observed along with
[Fe3(CO)8PPh3(m3-Te)2] and [Fe2(CO)5PPh3( -Te2)] (Scheme 1).
Compounds 1 and 2 were found to be stable in solid state under
inert atmosphere but gradually decompose in air. Suitable single
crystals of 1 and 2 were grown from hexane/dichloromethane
solvent mixture and their structures were established crystallo-
graphically. The IR spectra of 1 and 2 display a carbonyl stretching
h -
5-C5H5)(PPh3)(h1
¼
S
m
m
m
m
ꢀ
responding bond distances of the coordinated acetylenic bond in [{m-
ꢀ
SeC(H)]C(Ph)S}(CO)6Fe2] (1.293(13) A) [24], [{
Se}(CO)6Fe2] (1.331(7) A) [25], [{
m
-SeC(H)]C(Ph)
ꢀ
m-SeC(H)]C(Ph)Te}(CO)6Fe2]
ꢀ
Fig. 1. ORTEP diagram of compound 1 with 50% probability ellipsoids: Selected bond lengths (A) and bond angles (deg): Fe(1)eFe(2) ¼ 2.5323(9), Ru(1)eC(15) ¼ 1.843(5), Ru(1)e
C(1)
¼
2.071(5), C(1)eC(2)
¼
1.328(6), C(2)eC(3)
¼
1.481(6), Se(1)eC(1)
¼
1.993(4), Se(2)eC(2)
¼
1.980(4), Fe(1)eSe(1)
¼
2.3897(8), Fe(1)eSe(2)
¼
2.3727(9), Fe(2)e
Se(1) ¼ 2.3793(9), Fe(2)eSe(2) ¼ 2.3705(8) and O(1)eC(15)eRu(1) ¼ 173.5(5), C(1)eSe(1)eFe(1) ¼ 101.62(13), C(1)eSe(1)eFe(2) ¼ 105.38(14), C(2)eSe(2)eFe(2) ¼ 103.73(13),
C(2)eSe(2)eFe(1) ¼ 98.99(14). Se(2)eFe(1)eSe(1) ¼ 79.81(3), Se(2)eFe(2)eSe(1) ¼ 80.07(3).

P. Mathur et al. / Journal of Organometallic Chemistry 731 (2013) 55e60
57
ꢀ
Fig. 2. ORTEP diagram of compound 2 with 50% probability ellipsoids: Selected bond lengths (A and bond angles (deg): Fe(1)eFe2) ¼ 2.6136(19), Ru(1)eC(7) ¼ 2.023(10), Ru(1)e
Te(2) ¼ 2.7424(10), Ru(1)eTe(1) ¼ 2.7425(9),C(7)eC(8) ¼ 1.215(12), Fe(1)eTe(1) ¼ 2.5468(17), Fe(1)eTe(2) ¼ 2.5505(16), Fe(2)eTe(2) ¼ 2.5153(14), Fe(2)eTe(1) ¼ 2.5724(15) and
C(7)eC(8)eC(9) ¼ 176.6(10), Te(2)eRu(1)eTe(1) ¼ 66.21(2), Te(1)eFe(1)eTe(2) ¼ 71.99(4), Te(2)eFe(2)eTe(1) ¼ 72.14(4).
ꢀ
ꢀ
(1.31(1) A) [26], [{
m
-TeC(H)]C(Ph)Te}(CO)6Fe2] (1.34(1) A) [21],
the apical site. Compound 2 in contrast consists of an open Fe2Te2
butterfly with the Ru atom bridging the Te wing-tips (Fig. 2).
ꢀ
[{m
-SeC(H)]C(2-Th)Se}(CO)6Fe2] (1.306(14) A) [27], and [{
SC(C^CCH3)]C(H)Te}-(CO)6Fe2] (1.31(1) A) [28]. The FeeFe bond
distance of 2.5323(9) A in 1 is shorter than the corresponding dis-
tance in [{
m-
ꢀ
The structure of 2 is comparable with [(CO)6Fe2(
m-TeCH2Te)]
ꢀ
[29] and [( -C8H12)Pt(m3-Te)2Fe2(CO)6] [30]. FeeFe bond distance of
p
ꢀ
ꢀ
m
-TeC(H)]C(Ph)Te}(CO)6Fe2] (2.571(4) A) [21], but com-
2.6136(19) A is slightly longer than the corresponding distance in
ꢀ
ꢀ
parable with the 2.539(5) A in [{
m
-SeC(H)]C(Ph)Te}(CO)6Fe2] [26]
-SeC(H)]C(2-Th)Se}(CO)6Fe2] [23]. It is
[{ -SeC(H)]C(Ph)
m
-TeC(H)]C(Ph)Te}(CO)6Fe2] (2.571(4) A) [21], [{
m
ꢀ
ꢀ
and 2.513(9)
similar to the 2.501(3) A in [{
FeeSe bond lengths of 2.3897(8) A and 2.3705(8) A in 1 compare
A
in [{
m
Te}(CO)6Fe2] (2.539(5) A) [26] and [(CO)6Fe2 (m-TeCH2Te)] (2.587(2)
A) [30] but is comparable to 2.6120(19) A in [(
Te)2Fe2(CO)6] [30]. The FeeTe bond lengths 2.5468(17) A and
2.5153(14) A are slightly smaller than the 2.5889(15) A and
ꢀ
ꢀ
ꢀ
m
-SeC(H)]C(Ph)S}(CO)6Fe2] [24]. The
p-C8H12)Pt(m3-
ꢀ
ꢀ
ꢀ
ꢀ
ꢀ
ꢀ
well with the average FeeSe bond length of 2.382(2) A in [{
m-
ꢀ
ꢀ
ꢀ
SeC(H)]C(2-Th)Se}(CO)6Fe2] [27] and, 2.3792(9) A and 2.3901(9) in
[{ -SeC(H)]C(Ph)Se}(CO)6Fe2] [25]. The average SeeFeeSe bond
angle of 79.9ꢀ is similar to the average SeeFeeSe bond angle of 81.3ꢀ
and 81.4ꢀ in [{
-SeC(H)]C(2-Th)Se}(CO)6Fe2] [23] and [{ -SeC(H)]
2.5666(16) A in [(
p
-C8H12)Pt(m3-Te)2Fe2(CO)6] [30], and 2.551(2) A
ꢀ
m
and 2.544 (2) A in [(CO)6Fe2 (
m
-TeCH2Te)] [29]. The average TeeFee
Te bond angle of 72.1ꢀ is less than the average TeeFeeTe bond angle
of 79.1ꢀ and 75.4ꢀ in [(
-C8H12)Pt(m3-Te)2Fe2(CO)6] [30] and
[(CO)6Fe2 -TeCH2Te)] [29], respectively. The Cp and the PPh3 li-
m
m
p
C(Ph)Se}(CO)6Fe2] [25] respectively, but is greater than the average
(m
SeeFeeSe bond angle of 58ꢀ in the closed tetrahedron of
gands expectedly cause as the constriction of the butterfly as seen
[(CO)6Fe2(m-Se2)] [28]. This widening of bond angle is consistent
with an opening of the Fe2Se2 butterfly core to accommodate the
ruthenium-acetylide molecule.
in the TeeRueTe bridging angle of 66.21ꢀ which is much smaller
than the TeePteTe bond angle of 79.08(3)ꢀ in [(
p
-C8H12)Pt(m3
Te)2Fe2(CO)6] [30] and TeeCH2eTe bond angle 92.1(4)ꢀ in
[(CO)6Fe2( -TeCH2Te)] [29].
-
Formation of chalcogen bridged and acetylide-bearing mixed
metal clusters has been reported previously by our group from the
thermolytic reaction of [Fe3(CO)9(m3-E)2] clusters (E ¼ Se, Te) and
m
2.2. Reaction of [(
pentacarbonyl
h h
5- C5H5)Ru(PPh3)2( 1-C^CPh)] with iron
[(h
5-C5H5)M(CO)3(
h
1-C^CPh)] (M ¼ Mo, W) [20]. However, crystal
structure of only the selenium compound, [(h -
5-C5H5)MoFe2(m3
h
1-C^CPh)] has been reported; where it consists of a
In contrast to the reactions of [(
with [Fe3(CO)9(m3-E)2], even after extended photolysis of a THF
h h
5-C5H5)Ru(PPh3)2( 1-C^CPh)]
Se)2(CO)6(
[Fe2MoSe2] distorted square pyramidal core with the Mo atom at
Scheme 2. Thermolysis of [(h h
5-C5H5)Ru(PPh3)2( 1-C^CPh)] with Fe(CO)5.

58
P. Mathur et al. / Journal of Organometallic Chemistry 731 (2013) 55e60
ꢀ
Fig. 3. ORTEP diagram of compound 3 with 50% probability ellipsoids: Selected bond lengths (A) and bond angles (deg): C(9)eC(10) ¼ 1.462(3), C(8)eC(9) ¼ 1.331(3), Ru(1)e
C(8)
¼
2.1396(19), Ru(1)eC(9)
¼
2.133(2), Ru(1)eC(7)
¼
1.880(2), Fe(1)eC(7)
¼
2.369(2), Fe(1)eC(8)
¼
2.038(2), Fe(1)eC(9)
¼
2.083(2), Fe(2)eC(8)
¼
1.815(2), Fe(1)e
Fe(2) ¼ 2.6343(4), Ru(1)eFe(1) ¼ 2.6117(3), Ru(1)eFe(2) ¼ 2.6843(3) and Fe(1)eRu(1)eFe(2) ¼ 59.639(9), Ru(1)-eFe(1)eFe(2) ¼ 61.550(9), Fe(1)eFe(2)eRu(1) ¼ 58.811(9), O(7)e
C(7)eRu(1) ¼ 159.71(18), O(7)eC(7)eFe(1) ¼ 125.41(16).
solution containing the ruthenium acetylide and [Fe(CO)5] no new
product formation was observed.
[(
h
5-C5H5)Ru(PPh3)(C^CPh)] under photolytic condition or [(h5
1-C^CPh)] which can be obtained under thermolytic
-
C5H5)Ru(
h
When a toluene solution containing [(
h
5-C5H5)Ru(PPh3)2(h1
-
conditions. Both of these highly reactive species can be very good
synthons for cluster growth reactions.
C^CPh)] and [Fe(CO)5] was heated at 100 ꢀC for 7 h, under a ni-
trogen atmosphere, a new green coloured mixed metal cluster,
The acetylide unit acts as a five electron donor to the cluster
core. Compound 3 is an electron precise system having 48 cluster
valence electrons, but the formal electron counts for Ru1, Fe1 and
Fe2 are 19, 18 and 17 and surprisingly, it is the bond between the
19-electron Ru1 and the 18-electron Fe1 which is spanned by a
semibridging carbonyl.
[(h : :h
5-C5H5)RuFe2(CO)7(h2 h2 1-C]CPh)], 3 was obtained along
with [Fe(CO)4PPh3] (Scheme 2). Compound 3 was found to be stable
in solid state under inert atmosphere but it gradually decomposes
in air. The infrared spectrum of 3, shows CO stretching pattern in
the range 1960e2063 cmꢁ1, indicating the presence of semi-
bridging and terminal carbonyls. Suitable single crystals of 3 were
grown from hexane/dichloromethane solvent mixture and its
structure was established crystallographically.
3. Conclusion
The molecular structure of 3, shown in Fig. 3, consists of Fe2Ru
triangular core, capped by the acetylide moiety. While both Fe
atoms bear three terminal CO groups, a CO group bonded to Ru
shows a semi-bridging character towards Fe(1), as Ru(1)eC(7)e
O(7) bond angle is 159.71(18)ꢀ. Of the three metalemetal bonds,
CO bridged Ru(1)eFe(1) bond is the shortest, Fe(1)e
In conclusion, we have investigated the reactions of non-
carbonyl containing ruthenium acetylide [(h -
5-C5H5)Ru(PPh3)2(h1
C^CPh)] with [Fe3(CO)9(m3-E)2] (E ¼ Se or Te)] clusters and with
iron pentacarbonyl. The first example of an adduct of internal
acetylene was obtained in the reaction with [Fe3(CO)9(m3-Se2)];
whereas, with [Fe3(CO)9(m3-Te2)], a formal Ru insertion to the
Fe2Te2 butterfly and a formation of Fe2Te2Ru cluster was observed.
In the reaction of iron-pentacarbonyl, an acetylide stabilised Fe2Ru
mixed-metal cluster was obtained. It was also observed that, under
ꢀ
ꢀ
Fe(2) ¼ 2.6343(4) A, Ru(1)eFe(1) ¼ 2.6117(3) A and Ru(1)e
ꢀ
Fe(2) ¼ 2.6843(3) A. Important feature of compound 3 is the
change in bonding mode of acetylide towards ruthenium. Ruthe-
nium, which was initially bonded to acetylide in
h
1-fashion in
photolytic conditions [(
phosphine to give [(
5-C5H5)Ru(PPh3)(
der thermal conditions, it loses both phosphines, probably in a
stepwise manner, to give [(
5-C5H5)Ru( 1-C^CPh)], which can be
h
5-C5H5) Ru(PPh3)2(
h
1-C^CPh)] loses one
reactant, is bonded to acetylide in
(Ru(1)eC(8) ¼ 2.1396(19), Ru(1)eC(9) ¼ 2.133(2) A). This type of
h
2-fashion in the product
h
h
1-C^CPh)], whereas, un-
ꢀ
interchange has been established for binuclear [31] and poly-
h
h
nuclear [32e37] complexes containing
m
-alkynyl ligands. Fe(1) is
an important reactive unit in cluster growth reactions.
also bonded to acetylide in
h
2-fashion, (Fe(1)eC(8) ¼ 2.038(2),
ꢀ
Fe(1)eC(9) ¼ 2.083(2), Fe(2)eC(8) ¼ 1.815(2) A) whereas Fe(2)
4. Experimental section
acetylide bond is h1
.
The most significant part of the reaction is that the main product
3 does not contain any phosphine unit, which indicates, under the
harsher reaction condition, not one but both phosphines dissociate
4.1. General procedures
All reactions and manipulations were performed using standard
Schlenk line techniques under an inert atmosphere of pre-purified
nitrogen or argon. Solvents were purified, dried and distilled under
argon or nitrogen atmosphere prior to use. Infrared spectra were
from the [(
manner. This is a very interesting observation that [(
Ru(PPh3)2(
1-C^CPh)] can be a very good source of giving either
h
5-C5H5)Ru(PPh3)2(
h
1-C^CPh)], probably in a stepwise
5-C5H5)
h
h

P. Mathur et al. / Journal of Organometallic Chemistry 731 (2013) 55e60
59
Table 1
Crystal data and structure refinement for compound 1 to 3.
Compound
1
2
3
Empirical formula
Formula wt.
C38H25Fe2O7PRuSe2
995.24
C37H25Fe2O6PRuTe2
1064.51
C20H10Fe2O7Ru
575.05
Crystal system
Spacegroup
Triclinic
P-1
10.8550(10)
11.2875(11)
17.6763(7)
82.480(5)
82.019(5)
61.455(10)
1878.9(3)
Triclinic
P-1
8.5830(8)
11.1868(12)
20.4292(19)
96.924(8)
101.557(8)
104.830(9)
1826.9(3)
2
1.935
2.845
Monoclinic
P 21/n
15.0337(3)
8.6218(2)
15.7257(4)
90
104.995 (2)
90
1968.92(8)
4
ꢀ
a, A
ꢀ
b, A
ꢀ
c, A
a
, deg
, deg
b
g
, deg
3
ꢀ
Volume, A
Z
2
Dcalcd, Mg/m3
Abs coeff, mmꢁ1
F(000)
1.759
3.186
976
1.940
2.252
1128
1020
Crystal size, mm
0.33 ꢂ 0.26 ꢂ 0.21
0.38 ꢂ 0.33 ꢂ 0.28
0.33 ꢂ 0.26 ꢂ 0.21
q
range, deg
3.31e25.00
2.95e25.00
3.21e25.00
Index ranges
ꢁ10 ꢃ h ꢃ 12, ꢁ10 ꢃ k ꢃ 13,
ꢁ21 ꢃ l ꢃ 21
13670/6602 [R(int) ¼ 0.0371]
99.8%
6602/0/460
1.009
ꢁ10 ꢃ h ꢃ 7, ꢁ13 ꢃ k ꢃ 13,
ꢁ24 ꢃ l ꢃ 24
14299/6417 [R(int) ¼ 0.0786]
99.8%
6417/0/442
1.017
ꢁ17 ꢃ h ꢃ 16, ꢁ10 ꢃ k ꢃ 10,
ꢁ18 ꢃ l ꢃ 18
Reflections collected/unique
Completeness to
15282/3461 [R(int) ¼ 0.0258]
q
¼ 25
99.8%
3461/0/271
1.054
Data/restraints/parameters
Goodness-of-fit on F2
Final R indices [I > 2
R indices (all data)
Largest diff. peak and hole
s
(I)]
R1 ¼ 0.0379, wR2 ¼ 0.0802
R1 ¼ 0.0593, wR2 ¼ 0.0896
0.871 and ꢁ0.472 e Aꢁ3
R1 ¼ 0.0638, wR2 ¼ 0.1438
R1 ¼ 0.0897, wR2 ¼ 0.1694
1.938 and ꢁ1.420 e Aꢁ3
R1 ¼ 0.0199, wR2 ¼ 0.0470
R1 ¼ 0.0234, wR2 ¼ 0.0485
0.329 and ꢁ0.405 e Aꢁ3
recorded on Perkin Elmer FTIR spectrometer. NMR spectra were
recorded on Bruker AVANCE III/400 spectrometer with TMS as in-
ternal standard. Iron pentacarbonyl, and phenyl acetylene were
purchased from Fluka, and Aldrich, respectively, and were used
IR (nCO in hexane): 2072 cmꢁ1, 2033 cmꢁ1, 1992 cmꢁ1 indicate
the presence of terminal carbonyls. 1H NMR (
, CDCl3): 5.1 ppm (5H,
Cp protons), 7.11e7.52 ppm (20H, Ph protons). MS (m/z, ESþ):
1064.6 (Mþ). Anal. Calc. for C37H25Fe2O6PRuTe2: C, 41.75, H, 2.37.
Found: C, 41.32, H 2.52%.
d
without further purification. [(h h
5-C5H5)Ru(PPh3)2( 1-C^CPh)] [38]
Fe3(CO)9(m3-Se)2 [39] and [Fe3(CO)9(m3-Te)2] [40] were prepared as
described previously. Photochemical reactions were carried out in a
water cooled double-walled quartz vessel having a 125 W mercury
lamp manufactured by SAIC, India. TLC plates were purchased from
Merck (20 ꢂ 20 cm, silica gel 60 F254).
4.4. Synthesis of [(
h
5-C5H5)RuFe2(CO)7(h2
:
h2
:
h
1-C]CPh)] (3)
To a 10 ml toluene solution of [(
h
5-C5H5)Ru(PPh3)2(
h
1-C^CPh)]
(79 mg, 0.1 mmol), [Fe(CO)5] (0.2 ml,1.46 mmol) was added and the
mixture was heated at 100 ꢀC for 7 h under nitrogen atmosphere.
The solvent was removed under reduced pressure, and the residue
was subjected to chromatographic workup on silica gel TLC plates
by using dichloromethane/hexane solvent mixtures as eluent,
which afforded 12 mg (21%) of green coloured compound 3 along
with [Fe(CO)4PPh3].
4.2. Synthesis of [{m-SeC(CpRu(PPh3)(CO))]C(Ph)Se}(CO)6Fe2] (1)
To a solution of [(
h
5-C5H5)Ru(PPh3)2( 1-C^CPh)] (79 mg,
h
0.1 mmol), in THF, [Fe3(CO)9(m3-Se)2] (116 mg, 0.2 mmol) was added
and the solution was photolysed at 0 ꢀC for 30 min under a nitrogen
atmosphere. The solvent was removed under reduced pressure, and
the residue was subjected to a chromatographic workup on silica
gel TLC plates. Elution with dichloromethane/hexane solvent
IR
( , , ,
nCO in hexane): 2063 cmꢁ1 2043 cmꢁ1 2021 cmꢁ1
1995 cmꢁ1, 1960 cmꢁ1 indicate the presence of terminal and sem-
ibridging carbonyls. 1H NMR (
d, CDCl3): 5.22 ppm (5H, Cp protons),
mixture yielded 14 mg (14%) of compound
[Fe3(CO)8PPh3( -Se)2], [Fe2(CO)5PPh3( -Se)2] and SePPh3.
IR (nCO in hexane): 2073 cmꢁ1, 2035 cmꢁ1, 2027 cmꢁ1, 1993 cmꢁ1
indicate the presence of terminal carbonyls. 1H NMR (
, CDCl3):
1 along with
7.34e7.71 ppm (5H, Ph protons), MS (m/z, ESþ): 575.1 (Mþ). Anal.
m
m
Calc. for C20H10Fe2O7Ru: C, 41.77, H, 1.75. Found: C, 41.47, H, 1.88%.
d
5.04 ppm (5H, Cp protons), 7.17e7.42 ppm (20H, Ph protons). MS
(m/z, ESþ): 995.5 (Mþ). Anal. Calc. for C38H25Fe2O7PRuSe2: C, 45.86;
H, 2.53. Found: C, 45.49; H, 2.79%.
4.5. Crystal data of compound 1 to 3
Relevant crystallographic data and structure refinement details
are listed in Table 1. Suitable X-ray quality crystals of compounds 1,
2 and 3 were grown by slow evaporation of n-hexane and
dichloromethane. An Oxford Diffraction X calibur-S/Supernova
4.3. Synthesis of [(h h
5-C5H5)(PPh3)( 1-C^CPh)RuFe2(m3-Te)2(CO)6]
(2)
diffractometer were used for the cell determination and intensity
To a solution of [(
h
5-C5H5)Ru(PPh3)2(
h
1-C^CPh)] (79 mg,
data collection. Monochromatic Mo K
a
radiation (0.71359 A) was
ꢀ
0.1 mmol), in THF, [Fe3(CO)9(m3-Te)2] (136 mg, 0.2 mmol) was added
and the solution was photolysed at 0 ꢀC for 30 min under a nitrogen
atmosphere. The solvent was removed under reduced pressure, and
the residue was subjected to a chromatographic workup on silica
gel TLC plates by using dichloromethane/hexane solvent mixtures
as eluent, which afforded 9 mg (8%) of compound 2 along with
used for the measurements. Absorption corrections using multi j-
scans were applied. The structures were solved by direct methods
(SHELXS) and refined by full matrix least squares against Fo2 using
SHELXL-97 software [41]. Non-hydrogen atoms were refined with
anisotropic thermal parameters. All hydrogen atoms were
geometrically fixed and allowed to refine using a riding model. The
crystal and refinement data are summarized in Table 1.
[Fe3(CO)8PPh3(m-Te)2] and [Fe2(CO)5PPh3(m-Te2)].

60
P. Mathur et al. / Journal of Organometallic Chemistry 731 (2013) 55e60
[16] C.W. Pin, Y. Chi, C. Chung, A.J. Carty, S.-M. Peng, G.-H. Lee, Organometallics 17
Acknowledgements
(1998) 4146e4154.
[17] P. Mathur, M.O. Ahmed, A.K. Dash, M.G. Walawalkar, J. Chem. Soc. Dalton
Trans. (1999) 1795e1798.
[18] P. Mathur, M.O. Ahmed, A.K. Dash, M.G. Walawalkar, V.G. Puranik, J. Chem.
Soc. Dalton Trans. (2000) 2916e2922.
[19] P. Mathur, M.O. Ahmed, J.H. Kaldis, M.J. McGlinchey, J. Chem. Soc. Dalton
Trans. (2002) 619e629.
[20] P. Mathur, A.K. Bhunia, A. Kumar, S. Charrerjee, S.M. Mobin, Organometallics
21 (2002) 2215e2218.
P.M. is grateful to the Department of Science and Technology,
Government of India for support. A.R. and R.S.J. are grateful to CSIR,
Government of India for research fellowships.
Appendix A. Supplementary material
[21] Th. Fässler, D. Buchhloz, G. Huttner, L. Zsolnai, J. Organomet. Chem. 369 (1989)
297e308.
CCDC 898446, 898444, and 898445 contain the supplementary
crystallographic data for this paper. These data can be obtained free
of charge from The Cambridge Crystallographic Data Centre via
www.ccdc.cam.ac.uk/data_request/cif.
[22] P. Mathur, A.K. Dash, J. Cluster Sci. 9 (1998) 131e143.
[23] P. Mathur, A.K. Dash, M.M. Hossain, C.V.V. Satyanarayana, A.L. Rheingold,
G.P.A. Yap, L.M. Liable-Sands, J. Organomet. Chem. 543 (1997) 135e143.
[24] P. Mathur, A.K. Dash, M.M. Hossain, S.B. Umbarkar, C.V.V. Satyanarayana,
Y.-S. Chen, E.M. Holt, S.N. Rao, M. Soriano, Organometallics 15 (1996)
1356e1361.
References
[25] P. Mathur, M.M. Hossain, Organometallics 12 (1993) 2398e2400.
[26] P. Mathur, M.M. Hossain, S.B. Umbarkar, C.V.V. Satyanarayana, S.S. Tavale,
V.G. Puranik, Organometallics 14 (1995) 959e963.
[27] P. Mathur, M.M. Hossain, S.N. Datta, R.-K. Kondru, M.M. Bhadbhade, Organ-
ometallics 13 (1994) 2532e2535.
[28] C.F. Campana, F. Lo, L.F. Dahl, Inorg. Chem. 18 (1979) 3060e3064.
[29] P. Mathur, V.D. Reddy, R. Bohra, J. Organomet. Chem. 401 (1991) 339e346.
[30] A.A. Pasynskii, N.I. Semenova, Yu.V. Torubaev, P.V. Belousov, K.A. Lyssenko,
Zh.V. Dobrokhotova, Russ. Chem. Bull. Int. Ed. 50 (2001) 2215e2220.
[31] M. Akita, M. Terada, S. Oyama, Y. Morooka, Organometallics 9 (1990) 816e
825.
[1] K.A. Williams, A.J. Boydston, C.W. Bielawski, Chem. Soc. Rev. 36 (2007) 729e744.
[2] K. Onitsuka, A. Shimizu, S. Takahashi, Chem. Commun. (2003) 280e281.
[3] M.S. Khan, A.K. Kakkar, S.L. Ingham, P.R. Raithby, J. Lewis, B. Spencer,
F. Wittmann, R.H. Friend, J. Organomet. Chem. 472 (1994) 247e255.
[4] C.W. Faulkner, S.L. Ingham, M.S. Khan, J. Lewis, N.J. Long, P.R. Raithby,
J. Organomet. Chem. 482 (1994) 139e145.
[5] A. Abe, N. Kimura, S. Tabata, Macromolecules 24 (1991) 6238e6243.
[6] H.B. Fyfe, M. Mlekuz, D. Zergarian, N.J. Taylor, T.B. Marder, Chem. Commun.
(1991) 188e190.
[7] G. Gia, N.C. Payne, J.J. Vittal, R.J. Puddephatt, Organometallics12 (1993) 4771e4778.
[8] C.E. Powell, M.G. Humphrey, Coord. Chem. Rev. 248 (2004) 725e756.
[9] S.R. Marder, J.E. Sohn, G.D. Stucky, ACS Symp. Ser. 605 (1991) 455 (and ref-
erences therein).
[10] P.N. Prasad, D.J. Williams, Nonlinear Optical Effects in Molecules and Poly-
mers, Wiley, New York, 1991.
[11] P. Blenkiron, G.D. Enright, A.J. Carty, Chem. Commun. (1997) 483e484.
[12] Y. Chi, A.J. Carty, P. Blenkiron, E. Delgado, G.D. Enright, W. Wang, S.-M. Peng,
G.-H. Lee, Organometallics 15 (1996) 5269e5271.
[13] C.-H. Wu, Y. Chi, S.-H. Peng, G.-H. Lee, J. Chem. Soc. Dalton Trans. (1990)
3025e3031.
[14] E. Delgado, Y. Chi, W. Wang, G. Hogarth, P.J. Low, G.D. Enright, S.-M. Peng, G.-
H. Lee, A.J. Carty, Organometallics 17 (1998) 2936e2938.
[15] A.J. Carty, G. Hogarth, G. Enright, G. Frapper, Chem. Commun. (1997) 1883e1884.
[32] Y. Chi, B.-J. Liu, G.-H. Lee, S.-M. Peng, Polyhedron 8 (1989) 2003e2006.
[33] D.-K. Hwang, Y. Chi, S.M. Peng, G.H. Lee, Organometallics
2709e2718.
9 (1990)
[34] L.J. Farrugia, S.E. Rae, Organometallics 11 (1992) 196e206.
[35] P.M. Fritz, K. Polborn, M. Steimann, M. Beck, Chem. Ber. 122 (1989) 889e891.
[36] G.A. Koutsantonis, J.P. Selegue, J.G. Wang, Organometallics 11 (1992)
2704e2708.
[37] P. Mathur, A.K. Bhunia, C. Srinivasu, S.M. Mobin, J. Organomet. Chem. 670
(2003) 144e150.
[38] M.I. Bruce, C. Hameister, A.G. Swincer, R.C. Wallis, Inorg. Synth. 21 (1982) 82.
[39] W. Hieber, J. Gruber, Z. Anorg. Allg. Chem. 296 (1958) 91e103.
[40] D.A. Lesch, T.B. Rauchfuss, Inorg. Chem. 20 (1981) 3583e3585.
[41] SHELXL97 G.M. Sheldrick, Acta Crystallogr. A64 (2008) 112e122.