Syntheses, characterization, and electrochemistry of compounds containing 1-diphenylphosphino-1′-(di-tert-butylphosphino)ferrocene (dppdtbpf)

Article abstract of DOI:10.1016/j.jorganchem.2014.09.016

The reaction of copper(I) salts CuX (X = Cl, Br, I, CN, SCN), [Cu(CH₃CN)₄]PF₆ with 1-diphenylphosphino-1′-di-tert-butylphosphinoferrocene (dppdtbpf) in 1:1 M ratio in DCM-MeOH (50:50 V/V) at room temperature afforded mono and binuclear compounds having formula [Cu₂(μ-Cl)₂(κ²-P,P-dppdtbpf)₂] (1), [Cu₂(μ-Br)₂(κ²-P,P-dppdtbpf)₂] (2) [Cu₂(μ-I)₂(κ²-P,P-dppdtbpf)₂] (3), [Cu₂(μ-CN)₂(κ²-P,P-dppdtbpf)₂] (4), [Cu₂(μ₂-SCN)₂(κ²-P,P-dppdtbpf)₂] (5), and [Cu(κ²-P,P-dppdtbpf)(CH₃CN)₂]PF₆ (6). Reacting palladium(II) complex [Pd(C₆H₅CN)₂Cl₂] with dppdtbpf gave mononuclear compound [Pd(κ²-P,P-dppdtbpf)Cl₂] (7). The reaction of dppdtbpf with sulfur powder under reflux in chloroform afforded a ferrocene diphosphine disulfide dppSdtbpSf (8). All of the synthesized compounds were characterized by elemental analyses, IR, ¹H and ³¹P NMR, ESI-MS and electronic absorption spectroscopy. Molecular structures for the compounds 5, 6, 7 and 8 were determined crystallographically. Compound 5 exists as centrosymmetric dimer in which the two copper atoms are bonded to two dppdtbpf ligands and two bridging thiocyanate groups in μ₂-manner. In cationic compound 6, the copper atom is coordinated to one dppdtbpf ligand in κ²-manner and two acetonitrile molecules, whereas in 7, the palladium(II) adopted cis square-planar geometry by coordinating to one dppdtbpf ligand in κ²-manner and two chlorine atoms. Compound 8 revealed a sandwiched structure with both phosphine groups sulfurized. The electrochemical properties of 1-6 were studied by cyclic voltammetry. Compounds 1-6 exhibited moderately weak to strong luminescence properties, however compounds 7 and 8 are non-emissive in the solution state.

Full text of DOI:10.1016/j.jorganchem.2014.09.016

Journal of Organometallic Chemistry 772-773 (2014) 202e209
Contents lists available at ScienceDirect
Journal of Organometallic Chemistry
journal homepage: www.elsevier.com/locate/jorganchem
Syntheses, characterization, and electrochemistry of compounds
containing 1-diphenylphosphino-10-(di-tert-butylphosphino)
ferrocene (dppdtbpf)
,
Manoj Trivedi a *, Sanjeev Kumar Ujjain a, Gurmeet Singh a, Abhinav Kumar b,
,
**
Santosh Kumar Dubey c, Nigam P. Rath d
a Department of Chemistry, University of Delhi, Delhi 110007, India
b Department of Chemistry, University of Lucknow, Lucknow 226007, India
c Department of Chemistry, University College, Kurukshetra University, Kurukshetra 136119, India
d Department of Chemistry & Biochemistry and Centre for Nanoscience, University of Missouri-St. Louis, One University Boulevard, St. Louis,
MO 63121-4499, USA
a r t i c l e i n f o
a b s t r a c t
Article history:
The reaction of copper(I) salts CuX (X ¼ Cl, Br, I, CN, SCN), [Cu(CH3CN)4]PF6 with 1-diphenylphosphino-
10-di-tert-butylphosphinoferrocene (dppdtbpf) in 1:1 M ratio in DCMeMeOH (50:50 V/V) at room
Received 20 May 2014
Received in revised form
7 September 2014
Accepted 10 September 2014
Available online 19 September 2014
temperature afforded mono and binuclear compounds having formula [Cu2(
[Cu2( -Br)2( -I)2( -CN)2(
2-P,P-dppdtbpf)2] (2) [Cu2( 2-P,P-dppdtbpf)2] (3), [Cu2(
[Cu2(m2-SCN)2(
2-P,P-dppdtbpf)2] (5), and [Cu( 2-P,P-dppdtbpf)(CH3CN)2]PF6 (6). Reacting palladium(II)
complex [Pd(C6H5CN)2Cl2] with dppdtbpf gave mononuclear compound [Pd(
2-P,P-dppdtbpf)Cl2] (7). The
m
-Cl)2(
k
2-P,P-dppdtbpf)2] (1),
k
2-P,P-dppdtbpf)2] (4),
m
k
m
k
m
k
k
k
reaction of dppdtbpf with sulfur powder under reflux in chloroform afforded a ferrocene diphosphine
disulfide dppSdtbpSf (8). All of the synthesized compounds were characterized by elemental analyses, IR,
1H and 31P NMR, ESI-MS and electronic absorption spectroscopy. Molecular structures for the compounds
5, 6, 7 and 8 were determined crystallographically. Compound 5 exists as centrosymmetric dimer in
which the two copper atoms are bonded to two dppdtbpf ligands and two bridging thiocyanate groups in
Keywords:
1-Diphenylphosphino-10-di-tert-
butylphosphinoferrocene
Copper compound
Palladium compound
dppSdtbpSf
m2-manner. In cationic compound 6, the copper atom is coordinated to one dppdtbpf ligand in
and two acetonitrile molecules, whereas in 7, the palladium(II) adopted cis square-planar geometry by
coordinating to one dppdtbpf ligand in
2-manner and two chlorine atoms. Compound 8 revealed a
k
2-manner
X-ray
Weak interaction
k
sandwiched structure with both phosphine groups sulfurized. The electrochemical properties of 1e6
were studied by cyclic voltammetry. Compounds 1e6 exhibited moderately weak to strong luminescence
properties, however compounds 7 and 8 are non-emissive in the solution state.
© 2014 Elsevier B.V. All rights reserved.
Introduction
Cullen et al. initially reported 1-diphenylphosphino-10-di-tert-
butylphosphinoferrocene (dppdtbpf) in 1985 [31] but this system
During the last four decades, ferrocenyl diphosphines have
received significant research interest due to their extensive appli-
cations as ligands for a wide variety of transition metal catalysed
transformations [1e10]. The symmetrically substituted 1,10-
bis(phosphino)ferrocenes have seen unremitting growth [11e29]
but closely related unsymmetrical 1,10-bis(phosphino)ferrocenes
have not been given equivalent consideration [30e35]. Although
has received little attention [36]. Since, the phosphorus donors in
dppdtbpf are bonded to two different aliphatic and aromatic rings
therefore they may act as a type (II) hemilabile ligand systems [37].
Till date the metal complexes containing dppdtbpf as a ligand are
sporadic, the main examples include [PdCl2(dppdtbpf)] [31,36],
[Rh(PeP)NBD]ClO4 [30], [NiCl2(dppdtbpf)] [36], [PtCl2(dppdtbpf)]
[36], and [(AuCl)2dppdtbpf] [36]. In majority of studies where the
compound [Rh(PeP)(NBD)]ClO4 [(PeP ¼ dppf, dtbpf, or dppdtbpf)
was used as the catalyst precursor for catalytic hydrogenation of a
series of olefins with no clear trends were observed. However, it was
found that the dppf and dppdtbpf compounds gave similar results,
which were superior to dtbpf analogue in terms of induction time
* Corresponding author. Tel.: þ91 (0) 9811730475.
** Corresponding author. Tel.: þ1 314 516 5333.
E-mail addresses: manojtri@gmail.com (M. Trivedi), rathn@umsl.edu (N.P. Rath).
http://dx.doi.org/10.1016/j.jorganchem.2014.09.016
0022-328X/© 2014 Elsevier B.V. All rights reserved.

M. Trivedi et al. / Journal of Organometallic Chemistry 772-773 (2014) 202e209
203
and period for complete uptake of hydrogen. In another investiga-
Results and discussion
tion the catalytic activity of [Ni(dppdtbpf)(COD)] was examined for
the isomerization of 2-methyl-3-butenenitrile using either ZnCl2 or
BEt3 as the co-catalyst [38]. This study suggests that the asymmetric
steric and/or electronic properties of dppdtbpf can have a major
impact on reactivity. When BH3 was used as the co-catalyst,
[Ni(COD)dppdtbpf] had a higher selectivity for the formation of 3-
pentenenitrile than either the dppf or 1,10-bis(diisopropylphos-
phino)ferrocene (dippf) analogues. The stoichiometric reaction of
[Ni(dppdtbpf)(COD)], ZnCl2, and 2-methyl-3-butenenitrile yielded a
compound in which the -PtBu2 group was bonded to Zn and the
ePPh2 group remains bonded to Ni. Recently another incentive to
study copper(I) compounds of 1-diphenylphosphino-10-di-tert-
butylphosphinoferrocene had emerged from the findings that no
report has been published till date for the synthesis and structural
details of its compounds with simple salts, particularlycopper(I) and
theirapplication in catalysis (CeC or CeO bond formations) [39e41].
Surprisingly, only a few reports have been published containing
unsymmetrical 1,10-bis(phosphino)ferrocenes with the late transi-
tion metals [30e36]. During the course of our current study con-
cerning with the interaction of different copper(I) salts CuX (X ¼ Cl,
Br, I, CN, SCN), [Cu(CH3CN)4]PF6 and palladium(II) complex
[Pd(C6H5CN)2Cl2] with dppdtbpf and to assist in our understanding
of the Cu(I) and Pd(II) species present in solid and solution states,
herein we report the synthesis, spectroscopic characterization and
Synthesis
Reaction of the copper(I) salts CuX (X ¼ Cl, Br, I, CN, SCN),
[Cu(CH3CN)4]PF6 with 1-diphenylphosphino-10-di-tert-butylphos-
phinoferrocene (dppdtbpf) in 1:1 M ratio in DCM-MeOH (50:50 V/
V) under refluxing conditions gave mono and binuclear compounds
[Cu2(
m-X)2(
k
2-P,P-dppdtbpf)2] (X ¼ Cl(1), Br(2), I(3), CN(4), SCN(5)),
[Cu(k
2-P,P-dppdtbpf)(CH3CN)2]PF6 (6) in high yields. Upon treat-
ment of palladium(II) complex [Pd(C6H5CN)2Cl2] with dppdtbpf
gave the mononuclear compound [Pd(
k
2-P,P-dppdtbpf)Cl2] (7). On
the other hand, reaction of dppdtbpf ligand with sulfur powder in
refluxing condition in chloroform gave dppSdtbpfS (8) in reason-
ably good yield (Scheme 1). The compounds under study are air
stable, non-hygroscopic solids and soluble in dimethylformamide,
dimethylsulfoxide and halogenated solvents but insoluble in pe-
troleum ether and diethyl ether.
Characterization
All the compounds have been characterized by elemental ana-
lyses, spectral and electrochemical studies. Analytical data of 1e8
confirmed their respective formulations. More information about
composition of compounds has also been obtained by ESI-MS
spectrometric studies. The positions of various peaks and overall
fragmentation patterns strongly support proposed formulation of
the respective compounds. IR spectra of the compounds 4 and 5
display characteristic bands corresponding to the bridging CN and
SCN groups at 2112 cmꢀ1 and 2107 cmꢀ1, respectively. However, the
electrochemistry of copper(I) and palladium(II) compounds [Cu2(
m
-
X)2(
k
2-P,P-dppdtbpf)2] (X ¼ Cl(1), Br(2), I(3), CN(4), SCN(5)), [Cu(k2
-
P,P-dppdtbpf)(CH3CN)2]PF6(6),
[Pd(k
2-P,P-dppdtbpf)Cl2]
(7),
respectively. We also report the synthesis, and spectroscopic char-
acterization of a ferrocene diphosphine disulfide dppSdtbpSf (8).
Scheme 1. Synthetic routes for the compounds 1e8.

204
M. Trivedi et al. / Journal of Organometallic Chemistry 772-773 (2014) 202e209
presence of single nC≡N and nSCN bands are indicative of the pres-
ence of only one type of cyanide and thiocyanide bridges between
copper(I) atoms, which is in accordance with the compounds re-
ported in literature for bridging pseudohalide groups [42e45].
Compound 6 display bands at 845 cmꢀ1 and 2249 cmꢀ1 due to the
presence of counter ion PF6- and acetonitrile nC≡N, respectively. In 8
the band at 665 cmꢀ1 indicates the presence of P]S groups, which
is in good agreement with the literature values [46,47]. 1H and 31
{1H} NMR spectral data summarized in experimental section
strongly support formation of these compounds. The
5-C5H4
protons of dppdtbpf ligand show four singlets in the range
4.60e4.05 ppm in compounds 1, 3, 4, 5, and 6 (See F-1 to F-5
Supporting material). However, in the 1H NMR spectra of the
compound and 7,
5-C5H4 protons exhibit multiplets at
4.15e4.20 ppm and two singlets in the range of 4.29e4.40 ppm
(See F-6 Supporting material). The phenyl and tert-butyl protons of
dppdtbpf ligand were observed as multiplets at 8.40e7.04 ppm
and doublet at
1.30e1.42 ppm, respectively. The 31P{1H} NMR
P
h
d
2
h
d
d
Fig. 2. Emission spectra of the compounds 1e7 in CH2Cl2.
d
d
the extent of mixing due to the XLCT [49]. In the case of 4 and 5, the
CNꢀ and SCNꢀ anions may play a similar role as halogen in other
Cu(I) compounds. However, the possibilities of XLCT, CC, and LC
transitions may be ruled out since metalemetal bonding is negli-
gible and cyanide and thiocyanide have a fairly large band gap. Pike
et al. [52] reported that the emission band at 392 nm for CuCN
should be assigned to MC transitions of the type 3d / (4p, 4s).
They also reported that the peak broadening for (CuCN)20(pip)7
(pip ¼ piperazine), compared to that of CuCN, was due to the
incorporation of pip ligands and a heterogeneous array of copper(I)
centres. Considering the position and broad shape into account, the
emission in 4 and 5 are consistent with the MC transitions influ-
enced by the existence of dppdtbpf ligands. Compound 6 showed
weak luminescence at 492 nm upon excitation at 478 nm. This
luminescence is believed to originate predominantly from the
ligand-to-metal charge-transfer LMCT excited state [54]. Com-
pound 7 and 8 are non-emissive in CH2Cl2 solution.
spectra of the compounds 1e5 showed two resonances for the
dppdtbpf ligand (See F-8 to F-12 Supporting material). On the other
hand in 6 three signals are arising due to the presence of dppdtbpf
and counter ion PF-6 (See F-13 Supporting material). The 1H and 31
P
{1H} NMR spectra of 7 and 8 are within the expected range and
similar to the reported values (See F-7 & F-14 Supporting material)
[36].
Electronic absorption data of the compounds are summarized in
the experimental section and the spectra for 1e8 are depicted in
Fig. 1. Electronic absorption spectra of 1e8 displayed bands at
355e478 nm and 236e275 nm in dichloromethane solutions. The
lower-energy band at 355e478 nm has been assigned to the ded
transition. Higher-energy band at 236e275 nm has been assigned
to the intraligand charge transfer. All the compounds showed
photoluminescence at room temperature except 7 and 8 in
dichloromethane solution (Fig. 2). Upon excitation at their
respective lowest energy band maxima (355e478 nm) the com-
pounds exhibited moderate to strong emission (491e536 nm)
consistent with the previously reported compounds of copper(I)
[48e53]. We have tentatively assigned the emission of these Cu(I)
compounds as being combinations of metal-centred state modified
by the Cu/Cu interactions and MLCT or XLCT states due to the
broad emission spectra as dppdtbpf ligands do not show lumines-
cence in the range of 460e700 nm. The emission peaks for com-
pounds 1e5 are similar, which is in agreement with the similar
Cu2X2 inorganic subunits. For compounds 1e5, which have similar
structures but different X, the emission maxima at 502 nm (1, CuCl
type), 525 nm (2, CuBr type) and 502 nm (3, CuI type) can be
ascribed to the electron donating ability of X because the energies
of the HOMO or LUMO of the systems would certainly depend on
Molecular structure determination
In the present investigation four X-ray structures emerged for
the compound 5, 6, 7 and 8. Refinement details for all the structures
are summarized in Table 1. The molecular structures for the com-
pound 5, 6, 7 and 8 with atomic numbering scheme are presented
in Figs. 3e6 and selected bond lengths and angles are presented in
Table 2. Compounds 5, 6, 7 and 8 crystallize in the triclinic and
monoclinic systems with P‾1, P‾1, P21/c, P21/n space groups,
respectively. Compound 5 revealed to have a centrosymmetrical
dimeric unit with the two thiocyanate groups bridging the two
copper atoms. The tetrahedral coordination around the copper
atoms is defined by two P atoms of the chelating dppdtbpf ligand
[CueP bond lengths ¼ 2.2913(16) and 2.2991(18) Å] and two
thiocyanate groups. The P1eCueP2 bite angle is 112.82(6)ꢁ, which
is marginally larger than those found in analogous Cu(I) complexes
containing
[25,55e57]. The other coordination bond angles in 5 are rather
distorted [N(1)eCu(1)eP(1)
117.49(16)ꢁ, N(1)eCu(1)e
1,10-bis(diphenylphosphino)ferrocene
ligand
¼
P(2) ¼ 105.58(17)ꢁ, P(1)eCu(1)eS(1) ¼ 112.19(7)ꢁ, P(2)eCu(1)e
S(1) ¼ 110.54(7)ꢁ ]. This is because of the strained four-membered
Cu2(SCN)2 ring and due to steric hindrance of the dppdtbpf ligand.
The CueS, CueN and CueP bond distances are 2.417(2) Å,
2.023(6) Å and 2.2913(16)e2.2991(18) Å, respectively and are
comparable with other copper derivatives with ferrocenyl diphos-
phines [26,55,58]. The SeCeN bond angle is 179.0(6)ꢁ which
confirmed that thiocyanate groups are linearly coordinated to each
copper atom. The SeC and CeN bond distances fall in the range of
1.653(6) Å and 1.137(8) Å, respectively. These distances are within
Fig. 1. UVeVis spectra of compounds 1e8 in CH2Cl2.

M. Trivedi et al. / Journal of Organometallic Chemistry 772-773 (2014) 202e209
205
Table 1
Crystallographic data for 5, 6, 7, and 8.
5
6
7
8
Empirical formula
FW
Crystal system
space group
a, Å
C62H72N2P4S2Cu2Fe2
1271.99
Triclinic
P-1
9.2558(4)
13.3755(7)
13.4789(7)
107.917(5)
98.640(4)
103.817(4)
1495.96(15)
1
C34H42N2P3F6CuFe
804.99
Triclinic
P-1
10.8315(10)
12.9592(13)
14.2692(13)
84.023(8)
84.411(7)
71.068(9)
1880.0(3)
2
C30H36Cl2P2FePd
691.68
Monoclinic
P21/c
15.1165(15)
8.8830(9)
21.431(3)
90.00
91.876(11)
90.00
C30H36FeP2S2
578.50
Monoclinic
P21/n
13.2011(13)
12.3774(9)
17.708(2)
90
102.801(11)
90
2821.5(5)
4
b, Å
c, Å
a
, deg
, deg
b
g
, deg
V, Å3
2876.2(6)
4
1.836
Z
dcalc, g cmꢀ3
1.412
1.393
1.664
4.608
1.362
0.814
m
, mmꢀ1
3.938
T, K
293 (2)
293(2)
293(2)
293(2)
R1 all
R1 [I > 2
wR2
wR2 [I > 2
GoF
0.0599
0.0428
0.1008
0.0908
0.1460
0.0982
0.2640
0.2285
0.0504
0.0391
0.0697
0.0666
0.0527
0.0376
0.0847
0.0764
1.051
s
(I)]
s(I)]
1.009
1.020
1.111
the reported range [26,55,58]. The two substituted Cp rings in the
dppdtbpf ligand in 5 adopt the antiperiplanar staggered confor-
mation [Cp(centroid)/Fe/Cp(centroid) ¼ 177.60ꢁ], which de-
termines the conformational chirality of the Cp2Fe fragment.
Crystal packing in 5 is stabilised by CeH/S hydrogen bond in-
teractions. The H-bonding distances for CeH/S interactions are in
the range of 2.61e2.80 Å (See F-15 Supporting material).
Compound 6 posses distorted tetrahedral geometry around
Cu(1) consisting of two P atoms of the chelating dppdtbpf ligand
[Cu(1)eP(1) ¼ 2.311(3) Å, Cu(1)eP(2) ¼ 2.321(3) Å] and two
acetonitrile molecules [Cu(1)eN(1)
¼
2.056(9) Å, Cu(1)e
N(2) ¼ 2.091(10) Å], with one additional hexafluorophosphate
anion in the apical position. The acetonitrile ligands are linear
[N(2)eC(33)eC(34) ¼ 177.4(14)ꢁ, N(1)eC(31)eC(32) ¼ 176.2(14)ꢁ]
and linearly coordinated to copper metal [C(31)eN(1)e
Cu(1)
¼
172.3(10)ꢁ, C(33)eN(2)eCu(1)
¼
172.8(10)ꢁ]. The
P1eCueP2 bite angle is 116.17(10)ꢁ, for the chelating dppdtbpf and
is very close to the expected value for this coordination. This bite
angle is larger than the analogous Cu(I) complexes comprising of
1,10-bis(diphenylphosphino)ferrocene ligand [25,55e57] but
smaller than that of the nitrate derivative [56], which is claimed to
Fig. 3. Perspective view of [Cu2(m2-SCN)2(k
2-P,P-dppdtbpf)2] with 30% ellipsoids. H
atoms are omitted for clarity.
Fig. 4. Perspective view of [Cu(
k
2-P,P-dppdtbpf)(CH3CN)2]PF6 with 30% ellipsoids. H
Fig. 5. Perspective view of [Pd(k
2-P,P-dppdtbpf)Cl2] with 30% ellipsoids. H atoms are
atoms and PF6 molecule are omitted for clarity.
omitted for clarity.

206
M. Trivedi et al. / Journal of Organometallic Chemistry 772-773 (2014) 202e209
There is no symmetry in the compound 8 to make half of the
molecule unique and the asymmetric unit is represented by a whole
molecule. The two substituted Cp rings in 8 adopt the antiperiplanar
staggered conformation [Cp(centroid)/Fe/Cp(centroid) ¼ 177.57ꢁ],
which determinesthe conformationalchiralityof theCp2Fe fragment.
The pattern of bond distances within the cyclopentadienyl rings
shows substituent-induced geometrical distortions with a mean CeC
bond length for the P]S substituted C atoms of 1.423 Å. In general,
closerthecarbonatomtothesubstitutedcarbon, thelongeristheCeC
bond length. It is clear from a comparison of 8 with the compounds
having the same chalcogen atoms, the deviations in bond lengths are
almost negligible [28,46,47,59e62]. The phosphorus atoms have
distorted tetrahedral geometries. The PeS bond lengths in 8 are
1.9519(10) Åe1.9708(10) Å, which show partial double bond char-
acter. These are within the range and comparable with ferrocenyl
diphosphines chalcogenides found in the literature [28,46,47,65e68].
The phosphoryl group in 8 is twisted from 180ꢁ which is sterically
favoured. Such arrangement is expected when one or both phos-
phoryl groups are uncoordinated or open bridging. However, there
are sufficient exceptions in the literature which show that the pre-
diction of the twist angle is by no means straightforward [69,70].
Crystal packing in 8 is stabilised by CeH/S hydrogen bond in-
teractions. The H-bond distances for CeH/S interactions are in the
range of 2.74e2.85 Å (See F-18 Supporting material).
Fig. 6. Perspective view of dppSdtbpSf with 30% ellipsoids. H atoms are omitted for
clarity.
have the largest bite angle. The other coordination bond angles are
rather distorted. The two substituted Cp rings in the dppdtbpf
ligand in 6 adopt the antiperiplanar staggered conformation
[Cp(centroid)/Fe/Cp(centroid) ¼ 176.38ꢁ], which determines the
conformational chirality of the Cp2Fe fragment.
Crystal packing in 6 is stabilised by CeH/F and CeH/N
hydrogen bond interactions. The H-bond distances for CeH/F and
CeH/N interactions are in the range of 2.27e2.51
Å and
2.678e2.918 Å, respectively (See F-16 Supporting material).
Electrochemistry
In compound 7, the palladium adopts a square planar geometry
with two P atoms from dppdtbpf ligand [Pd(1)eP(1) ¼ 2.2916(9) Å,
Pd(1)eP(2) ¼ 2.3181(8) Å] and two cis chlorine atoms [Pd(1)e
Cl(1) ¼ 2.3415(8) Å, Pd(1)eCl(2) ¼ 2.3393(9) Å]. This structure was
reported previously by Cullen et al., in 1985 [31]. The P1ePdeP2
bite angle is 101.37(3)ꢁ, which is smaller than other palladium
ferrocene diphosphine complexes, such as [PdCl2(dippf)] [59],
[PdCl2(dcypf)] [60], [PdCl2(dtbpf)] [61] but larger than
[PdCl2(dppf)] [30,31], [PdCl2(dmpf)] [62], [PdCl2(depf)] [63],
[PdCl2(dppr)] [64]. This can be attributed to the steric hindrance of
the bulky phenyl and t-butyl groups. The two substituted Cp rings
in the dppdtbpf ligand in 7 adopt the antiperiplanar staggered
conformation [Cp(centroid)/Fe/Cp(centroid) ¼ 179.08ꢁ], which
determines the conformational chirality of the Cp2Fe fragment.
Crystal packing in 7 is stabilized by CeH/Cl hydrogen bond
interactions. The contact distances for CeH/Cl interactions are in
the range of 2.48e2.67 Å (See F-17 Supporting material).
The electrochemical properties of newly synthesized com-
pounds were investigated by cyclic voltammetry in CH2Cl2 at room
temperature (r.t.) and the electrochemical data are presented in
Table 3. The presence of two kinds of redox active centres in the
compounds 1e6, i.e. iron(II), and copper(I), prompted us to study
the electrochemistry of these compounds in the region of þ2.0
to ꢀ2.0 V at scan rate of 100 mV sꢀ1, where the potentials are
referenced to Ag/Agþ (Fig. 7). The oxidation of 1 and 3e6 are quasi-
reversible. However, there appears to be some reversibility to the
reduction around ꢀ1.0 V in 2. The first oxidation process is repre-
sented by removal of one electron at 0.35e0.78 V vs. Fcþ/0. The next
oxidation wave at 1.12e1.30 V is in correspondence to the copper(I/
II) oxidation. The electrochemistry of compounds 7 and 8 has been
previously described by Nataro et al. [36]. We have found similar
findings, and it shows the one chemically and electrochemically
reversible wave.
Table 2
Selected bond lengths (Å), and bond angles (ꢁ) for 5, 6, 7 and 8.
5
6
7
8
Cu(1)eN(1) 2.013(3)
Cu(1)eN(1) 2.055(7)
Pd(1)eP(1) 2.2917(9)
S(1)eP(1) 1.9519(10)
Cu(1)eP(1) 2.2904(9)
Cu(1)eN(2) 2.082(8)
Pd(1)eP(2) 2.3183(9)
P(2)eS(2) 1.9708(10)
Cu(1)eP(2) 2.3005(10)
Cu(1)eS(1) 2.4178(10)
P(1)eC(15) 1.895(3)
Cu(1)eP(1) 2.310(2)
Cu(1)eP(2) 2.319(2)
P(1)eC(11) 1.920(9)
Pd(1)eCl(2) 2.3395(10)
Pd(1)eCl(1) 2.3416(9)
P(2)eC(27) 1.916(3)
P(1)eC(11) 1.816(3)
P(1)eC(17) 1.822(3)
P(2)eC(23) 1.875(3)
P(1)eC(11) 1.912(4)
P(1)eC(15) 1.916(9)
P(2)eC(23) 1.890(4)
P(2)eC(27) 1.885(3)
P(2)eC(19) 1.832(4)
P(2)eC(25) 1.836(4)
S(1)eC(31) 1.656(4)
P(2)eC(25) 1.832(7)
P(2)eC(19) 1.817(8)
P(1)eC(11) 1.818(4
P(1)eC(17) 1.834(4)
C(1)eP(1)eC(11)103.21(12)
C(1)eP(1)eC(17) 107.91(12)
C(1)eP(1)eS(1) 112.89(9)
C(17)eP(1)eS(1) 112.94(9)
C(11)eP(1)eS(1) 111.98(9)
C(11)eP(1)eC(17)107.30(12)
C(6)eP(2)eS(2) 111.52(10)
C(6)eP(2)eC(23) 108.48(13)
C(6)eP(2)eC(27) 102.88(13)
C(27)eP(2)eS(2) 111.05(10)
C(23)eP(2)eS(2) 110.84(10)
N(1)eC(31) 1.119(10)
N(2)eC(33) 1.136(10)
N(1)eCu(1)eN(2) 99.8(3)
N(1)eCu(1)eP(1) 114.1(2)
N(2)eCu(1)eP(1) 112.2(2)
N(1)eCu(1)eP(2) 109.7(2)
N(2)eCu(1)eP(2) 102.9(2)
P(1)eCu(1)eP(2) 116.36(8)
C(31)eN(1)eCu(1) 174.2(8)
C(33)eN(2)eCu(1) 173.4(8)
P(1)ePd(1)eP(2) 101.37(3)
P(1)ePd(1)eCl(2) 166.49(3)
P(2)ePd(1)eCl(2) 92.07(3)
P(1)ePd(1)eCl(1) 80.85(3)
P(2)ePd(1)eCl(1) 173.80(4)
Cl(2)ePd(1)eCl(1) 85.64(3)
N(1)eC(31)#1 1.144(4)
C(31)eN(1)#1 1.144(4)
N(1)eCu(1)eP(1) 117.50(9)
N(1)eCu(1)eP(2) 105.46(9)
P(1)eCu(1)eP(2) 112.82(3)
N(1)eCu(1)eS(1) 97.09(9)
P(1)eCu(1)eS(1) 112.22(4)
P(2)eCu(1)eS(1) 110.55(4)
C(31)#1eN(1)eCu(1)157.7(3)
N(1)#1eC(31)eS(1) 178.7(3)

M. Trivedi et al. / Journal of Organometallic Chemistry 772-773 (2014) 202e209
207
Table 3
following the standard procedures [71]. Copper(I) chloride, Cop-
per(I) bromide, Copper(I) iodide, Copper(I) cyanide, Copper(I)
thiocyanate, tetrakis(acetonitrile)copper(I)hexafluorophosphate,
bis(benzonitrile)dichloropalladium(II), sulfur and 1-diphenylpho-
Electrochemical data for 1e6 in dichloromethane solution/0.1 M [NBu4]ClO4 at
298 K.
Compound
Oxidationa
Reductionb
Epa/V vs. FcH0/þ
Epc/V vs. FcH0/þ
sphino-10-di-tert-butylphosphinoferrocene
(dppdtbpf)
(all
[Cu2(
[Cu2(
[Cu2(
[Cu2(
[Cu2(
m
m
m
m
m
-Cl)2(
-Br)2(
-I)2(
2-P,P-dppdtbpf)2] (3)
-CN)2(
2-P,P-dppdtbpf)2] (4)
-SCN)2(
2-P,P-dppdtbpf)2] (5)
k
2-P,P-dppdtbpf)2] (1)
2-P,P-dppdtbpf)2] (2)
0.78, 1.30
0.78, 1.20
0.57, 1.22
0.58, 1.12
0.35, 1.30
0.36, 1.28
ꢀ0.95, ꢀ1.58
ꢀ0.90, ꢀ1.59
ꢀ0.93, ꢀ1.64
ꢀ1.11, ꢀ1.57
ꢀ0.94, ꢀ1.56
ꢀ0.90, ꢀ1.41
Aldrich) were used as received. Elemental analyses were performed
on a Carlo Erba Model EA-1108 elemental analyzer and data for C, H
and N analyses were within 0.4% of calculated values. IR(KBr)
were recorded using PerkineElmer FT-IR spectrophotometer.
Electronic and emission spectra of the compounds 1e8 were ob-
tained on a Perkin Elmer Lambda-35 and Horiba Jobin Yvon Fluo-
rolog 3 spectrofluorometer, respectively. 1H and 31P NMR spectra
were recorded on a JEOL AL-400 FTNMR instrument using tetra-
methylsilane and phosphoric acid as an internal standards,
respectively. Mass spectral data were recorded using a Waters
micromass LCT Mass Spectrometer/Data system. Electrochemical
properties of the compounds 1e8 were measured by cyclic vol-
tammetry using platinum as counter and glassy carbon as working
electrodes and the supporting electrolyte was [NBu4]ClO4 (0.1 M) in
dichloromethane solution of 0.001 M of compounds 1e8 versus Ag/
k
k
k
k
[Cu(
k
2-P,P-dppdtbpf)(CH3CN)2]PF6 (6)
a
Epa is the anodic peak potential of the oxidation wave.
Epc is the cathodic peak potential of the reduction wave.
b
Conclusion
The work presented herein describes the reaction chemistry of
copper(I) halides and pseudohalides with dppdtbpf ligand, that re-
sults in the formation of binuclear species having general formula
[Cu2(m
-X)2(
k
2-P,P-dppdtbpf)2] (X ¼ Cl(1), Br(2), I(3), CN(4), and
SCN(5)). We have also reported the reactions of [Cu(CH3CN)4]PF6 and
AgCl at a scan rate of 100 mV sꢀ1
Synthesis
[Cu2( -Cl)2(
.
[Pd(C6H5CN)2Cl2] with dppdtbpf which gave mononuclear species
[Cu(k k
2-P,P-dppdtbpf)(CH3CN)2]PF6 (6), and [Pd( 2-P,P-dppdtbpf)Cl2]
(7), respectively. The reaction of dppdtbpf with sulfur powder
resulted in a ferrocene diphosphine disulfide dppSdtbpSf (8). To the
best of our knowledge compound 5 represents the first example of a
structurally characterized binuclear copper compound containing
dppdtbpf ligand. These compounds have been shown to exhibit
luminescence properties except 7 and 8, and the emission wave-
length was found to be similar in 1 to 5, which are in agreement with
their similar Cu2X2 inorganic subunits. Further work towards the
development of silver(I) and gold(I) compounds containing dppdtbpf
ligand is in progress in our laboratory.
m
k
2-P,P-dppdtbpf)2] (1)
1-diphenylphosphino-10-di-tert-butylphosphinoferrocene
(514 mg, 1 mmol) was added to a solution of copper(I) chloride
(99 mg, 1 mmol) in 30 mL CH3OH:CH2Cl2 (50:50 V/V). The resulting
mixture was refluxed for 24 h. Slowly, the colour of the solution
changed from orange to yellowish orange. The resulting solution
was evaporated to obtain yellowish orange solid, which was then
extracted with dichloromethane (50 mL). The addition of hexane
(100 mL) to this solution led to the isolation of yellowish orange
solid which was separated and washed with diethyl ether. Yield:
(0.858 g, 70%). Anal. Calc. for C60H72Cl2P4Cu2Fe2: C, 58.73; H, 5.87.
Experimental
Materials and physical measurements
Found: C, 58.83; H, 5.95. IR (cmꢀ1, KBr):
1171, 1154, 1096, 1029, 830, 805, 753, 716, 695, 531, 484, 452. 1H
NMR ( ppm, 400 MHz, CDCl3, 298 K): 7.63e7.04 (m, 20H, Ph),
4.60 (s, 4H, C5H4), 4.52 (s, 4H, C5H4), 4.41 (s, 4H, C5H4), 4.34 (s, 4H,
n
¼ 3433, 2925, 1637, 1438,
All the synthetic manipulations were performed under nitrogen
atmosphere. The solvents were dried and distilled before use by
d
d
Fig. 7. Cyclic voltammograms for the compound 1e6 in CH2Cl2/0.1 M [NBu4]ClO4 at 100 mV/s scan rate.

208
M. Trivedi et al. / Journal of Organometallic Chemistry 772-773 (2014) 202e209
C5H4), 1.41 (d, 3JH-P ¼ 51.2 Hz, 36H, eCH3). 31P{1H}:
d
27.96, ꢀ16.54.
C5H4), 4.39 (s, 4H, C5H4), 4.32 (s, 4H, C5H4), 4.05 (s, 4H, C5H4),1.40 (d,
UV/Vis: lmax (ε[dm3 molꢀ1 cmꢀ1]) ¼ 267(1630), 450(10,572). ESI-
MS (m/z): (Mþ) 1226.4.
3JH-P ¼ 13.9 Hz, 36H, CH3). 31P{1H}:
d
29.09, ꢀ14.54. UV/Vis: lmax
(ε[dm3 molꢀ1 cmꢀ1]) ¼ 275(4840), 470(9497). ESI-MS (m/z): 1271.2
(Mþ).
[Cu2(m-Br)2(k
2-P,P-dppdtbpf)2] (2)
This compound was prepared by a similar method (compound
1) except copper(I) bromide (143 mg, 1.0 mmol) was used in place
of copper(I) chloride. The resulting reddish yellow solution was
evaporated to give a reddish yellow solid which was then extracted
with 50 mL dichloromethane. The addition of hexane (100 mL) to
this solution led to the isolation of reddish yellow solid. This was
separated and washed with diethyl ether. Yield: (1.052 g, 80%).
Anal. Calc. for C60H72Br2P4Cu2Fe2: C, 54.75; H, 5.48. Found: C, 54.93;
[Cu(k
2-P,P-dppdtbpf)(CH3CN)2]PF6 (6)
1-Diphenylphosphino-10-di-tert-butylphosphinoferrocene
(514 mg, 1 mmol) was added slowly to a solution of CH3OH (15 mL),
and CH2Cl2 (15 mL) containing tetrakis(acetonitrile)copper(I) hex-
afluorophosphate (372 mg, 1 mmol). The resulting solution was
refluxed for 24 h. Slowly, colour of the solution changed from or-
ange to dark red colour. The resulting solution was filtered and
saturated with hexane and left for slow evaporation. Dark red
colour needle shape crystals suitable for X-ray studies were grown
after one week. Yield: (0.644 g, 80%). Anal. Calc. for
H, 5.65. IR(cmꢀ1, KBr):
1475, 1458, 1389, 1365, 1178, 1157, 1037, 932, 831, 815, 741, 606,
581, 547, 494, 471. 1H NMR (
ppm, 400 MHz, CDCl3, 298 K):
n
¼ 3448, 3356, 3094, 2941, 2895, 2862,1637,
d
C
34H42N2P3F6CuFe: C, 50.71; H, 5.22; N, 3.48. Found: C, 50.91; H,
5.31; N, 3.64. IR(cmꢀ1, KBr):
¼ 3099, 3071, 3048, 2249, 1381, 1169,
1102, 1075, 1037, 997, 916, 845, 749, 696, 538, 547, 488, 464, 430. 1H
NMR ( ppm, 400 MHz, CDCl3, 298 K): 7.63e7.24 (m,10H, Ph), 4.49
(s, 2H, C5H4), 4.45 (s, 2H, C5H4), 4.39 (s, 2H, C5H4), 4.19 (s, 2H, C5H4),
3
d
7.78e7.09 (m, 20H, Ph), 4.15e4.20 (m, 16H, C5H4), 1.30 (m, JH-
n
¼ 16.1 Hz, 36H, CH3). 31P{1H}:
d
28.96, ꢀ15.54. UV/Vis: lmax
P
(ε[dm3 molꢀ1 cmꢀ1]) ¼ 236(2082), 355(9096). ESI-MS (m/z): 1315.1
d
d
(Mþ).
3
1.99 (s, 6H, CH3), 1.42 (d, JH-P
¼
15.4 Hz, 18H, CH3). 31P
[Cu2(
m-I)2(
k
2-P,P-dppdtbpf)2] (3)
{1H}:
d
29.39, ꢀ19.74, ꢀ149.53(sep., PF6). UV/Vis: lmax
This compound was synthesized by using the same method as
mentioned for 1, using copper(I) iodide (190 mg, 1.0 mmol). The
resulting dark yellow solution was evaporated to dryness to give a
yellow solid which was then extracted with dichloromethane
(50 mL). The addition of hexane (100 mL) to this solution led to the
isolation of dark yellow solids. This was separated and washed with
diethyl ether. Yield: (0.986 g, 70%). Anal. Calc. for C60H72I2P4Cu2Fe2:
(ε[dm3 molꢀ1 cmꢀ1]) ¼ 255(4233), 478(9558). ESI-MS (m/z): 659.1
(Mþ).
[Pd(k
2-P,P-dppdtbpf)Cl2] (7)
1-Diphenylphosphino-10-di-tert-butylphosphinoferrocene
(514 mg, 1 mmol) was added slowly to a solution of CH3OH (15 mL),
and CH2Cl2 (15 mL) containing bis(benzonitrile)dichlor-
opalladium(II) (383 mg, 1 mmol). The resulting solution was
refluxed for 24 h. Slowly, colour of the solution changed from or-
ange to dark red colour. The resulting solution was filtered and
saturated with hexane and left for slow evaporation. Dark red
colour crystals suitable for X-ray studies were grown after one
week. Yield: (0.553 g, 80%). Anal. Calc. for C30H36Cl2P2PdFe: C,
C, 51.10; H, 5.11. Found: C, 51.31; H, 5.21. IR(cmꢀ1, KBr):
3356, 3094, 2941, 2895, 2862, 1637, 1475, 1458, 1389, 1365, 1178,
1157, 1037, 932, 831, 815, 741, 606, 581, 547, 494, 471. 1H NMR (
ppm, 400 MHz, CDCl3, 298 K): 7.67e7.32 (m, 20H, Ph), 4.48(s, 4H,
n
¼ 3448,
d
d
C5H4), 4.44(s, 4H, C5H4), 4.35(s, 4H, C5H4), 4.18 (s, 4H, C5H4), 1.30 (d,
3JH-P ¼ 12.4 Hz, 36H, CH3). 31P{1H}:
d
29.90, ꢀ12.84. UV/Vis: lmax
(ε[dm3 molꢀ1 cmꢀ1]) ¼ 270(1054), 452(8830). ESI-MS (m/z): 1409.2
52.09; H, 5.21. Found: C, 52.31; H, 5.21. IR(cmꢀ1, KBr):
n
¼ 3420,
(Mþ).
3350, 3093, 2940, 2890, 2860, 1470, 1450, 1380, 1175, 1150, 1030,
931, 855, 811, 740, 601, 580, 540, 461. UV/Vis: lmax
(ε[dm3 molꢀ1 cmꢀ1]) ¼ 268(1629), 452(9976). ESI-MS (m/z): 691.2
(Mþ).
[Cu2(m-CN)2(k
2-P,P-dppdtbpf)2] (4)
The same method as mentioned for 1, was used for the synthesis
of 4, using copper cyanide (89 mg, 1.0 mmol). The resulting yellow
solution was evaporated to dryness to give a solid residue which
was washed with diethyl ether, and dried under vacuo. Yield:
(0.784 g, 65%). Anal. Calc. for C62H72N2P4Cu2Fe2: C, 61.64; H, 5.97; N,
dppSdtbpSf (8)
Compound 8 was synthesized following the published proce-
dure reported by Nataro et al. [36]. Yield: (0.405 g, 70%). Anal. Calc.
for C30H36P2S2Fe: C, 62.28; H, 6.23; S,11.07. Found: C, 62.43; H, 6.35;
2.32. Found: C, 61.71; H, 6.01; N, 2.42. IR(cmꢀ1, KBr):
n
¼ 3412, 3346,
3094, 2941, 2895, 2862, 2112, 1655, 1475, 1458, 1389, 1311, 1165,
1157, 1037, 897, 818, 741, 696, 630, 545, 494. 1H NMR (
ppm,
400 MHz, CDCl3, 298 K): 7.69e7.09 (m, 20H, Ph), 4.42 (s, 4H, C5H4),
S, 11.05. IR (cmꢀ1, KBr):
n
¼ 3433, 2925, 1637, 1438, 1171, 1154, 1096,
1029, 830, 805, 753, 716, 697, 665, 543, 503, 484, 452. 1H NMR (
ppm, 400 MHz, CDCl3, 298 K): 7.71e7.41 (m, 10H, Ph), 4.38 (s, 2H,
d
d
d
d
3
4.28 (s, 4H, C5H4), 4.19 (s, 4H, C5H4), 4.10 (s, 4H, C5H4) 1.39 (d, JH-
C5H4), 4.45 (s, 2H, C5H4), 4.62 (s, 2H, C5H4), 4.81 (s, 2H, C5H4),
¼ 13.1 Hz, 36H, CH3). 31P{1H}:
d
22.17, ꢀ19.90. UV/Vis: lmax
1.22 (d, 3JH-P ¼ 15.4 Hz, 18H, eCH3). 31P{1H}:
d
77.66 (s, eP(S)tBu2),
lmax/nm, CH2Cl2,
P
(ε[dm3 molꢀ1 cmꢀ1]) ¼ 249(1622), 457(9932). ESI-MS (m/z): 1207.4
41.7
(s,
eP(S)Ph2).
UV/Vis:
(Mþ).
(ε[dm3 molꢀ1 cmꢀ1]) ¼ 375(9846).
[Cu2(m2-SCN)2(
k
2-P,P-dppdtbpf)2] (5)
X-ray crystallographic study
Compound 5 was synthesized using a similar method mentioned
for 1, using copper(I) thiocyanate (121 mg, 1 mmol). The resulting
orangeyellowsolutionwasevaporated todryness togive ayellowish
orange solid which was then extracted with 50 mL dichloromethane
and saturated with hexane and left for slow evaporation. Slowly,
yellow needle shaped crystals appeared. These were separated and
air dried. Yield: (1.017 g, 80%). Anal. Calc. for C62H72N2P4S2Cu2Fe2: C,
58.54; H, 5.66; N, 2.20; S, 5.03. Found: C, 58.71; H, 5.81; N, 2.22; S,
Intensity data sets for 5, 6, 7 and 8 were collected on Oxford X-
calibur S CCD area detector diffractometers using graphite mono-
chromatized Mo-Ka radiation at 293(2) K. The strategy for the data
collection was evaluated by using the CrysAlisPro CCD software.
The data were collected by the standard ’phi-omega scan tech-
niques, and was scaled and reduced using CrysAlisPro RED soft-
ware. The structures were solved by direct methods using SHELXS-
97, and refined by full matrix least-squares refinement with
SHELXL-97, refining on F2 [72]. The non-hydrogen atoms were
refined with anisotropic thermal parameters. All the hydrogen
5.13. IR(cmꢀ1, KBr):
1365,1164,1091,1024, 899, 831, 815, 741, 695, 581, 529, 484. 1H NMR
ppm, 400 MHz, CDCl3, 298 K): 7.62e7.36 (m, 20H, Ph), 4.42 (s, 4H,
n
¼ 3442, 2895, 2862, 2107, 1632, 1433, 1386,
(d
d

M. Trivedi et al. / Journal of Organometallic Chemistry 772-773 (2014) 202e209
209
[28] F.N. Blanco, L.E. Hagopian, W.R. McNamara, J.A. Golen, A.L. Rheingold,
C. Nataro, Organometallics 25 (2006) 4292e4300.
[29] V. Rampazzi, A. Massard, P. Richard, M. Picquet, P.L. Gendre, J.-C. Hierso,
ChemCatChem 4 (2012) 1828e1835.
atoms were treated using appropriate riding models. The computer
program PLATON was used for analysing the interaction and
stacking distances [73,74].
[30] W.R. Cullen, T.J. Kim, F.W.B. Einstein, T. Jones, Organometallics 4 (1985)
346e351.
[31] I.R. Butler, W.R. Cullen, T.J. Kim, S.J. Rettig, J. Trotter, Organometallics 4 (1985)
972e980.
Acknowledgements
ꢀ
ꢀ
ꢀ
ꢀ
ꢀ
ꢂ
[32] P. Stĕpnicka, I. Císarova, J. Schulz, Organometallics 30 (2011) 4393e4403.
We gratefully acknowledge financial support by the Department
of Science and Technology, New Delhi (Grant No. SR/FT/CS-104/
2011). We also thank to the Director, USIC, University of Delhi,
Delhi, for providing analytical, spectral and Single Crystal X-ray
Diffraction facilities. Special thanks are due to Professor D.S. Pan-
dey, Banaras Hindu University, Varanasi, India, Dr. Sanjit Koner,
IISER, Bhopal, India and Professor Josef Michl, University of Colo-
rado, USA for their kind encouragement.
ꢀ
ꢀ
ꢂ
[33] P. Stĕpnicka, K. Skoch, I. Císarova, Organometallics 32 (2013) 623e635.
[34] K.M. Gramigna, J.V. Oria, C.L. Mandell, M.A. Tiedemann, W.G. Dougherty,
N.A. Piro, W.S. Kassel, B.C. Chan, P.L. Diaconescu, C. Nataro, Organometallics 32
(2013) 5966e5979.
ꢀ
ꢀ
ꢀ
ꢂ
ꢀ
[35] K. Skoch, I. Císarova, P. Stĕpnicka, Inorg. Chem. 53 (2014) 568e577.
[36] S.L. Kahn, M.K. Breheney, S.L. Martinak, S.M. Fosbenner, A.R. Seibert,
W.S. Kassel, W.G. Dougherty, C. Nataro, Organometallics 28 (2009)
2119e2126.
[37] P. Braunstein, F. Naud, Angew. Chem. Int. Ed. 40 (2001) 680e699.
[38] A. Acosta-Ramirez, M. Munoz-Hernandez, W.D. Jones, J.J. Garcia, Organome-
tallics 26 (2007) 5766e5769.
Appendix A. Supplementary material
ꢂ
ꢁ
[39] M. Beauperin, E. Fayad, R. Amardeil, H. Cattey, P. Richard, S. Brandes,
P. Meunier, J.-C. Hierso, Organometallics 27 (2008) 1506e1513.
ꢂ
[40] M. Beauperin, A. Job, H. Cattey, S. Royer, P. Meunier, J.-C. Hierso, Organome-
CCDC 928116, 977182, 977184, and 963134 contain the supple-
mentary 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.
tallics 29 (2010) 2815e2822.
[41] J.-C. Hierso, R. Smaliy, R. Amardeil, P. Meunier, Chem. Soc. Rev. 36 (2007)
1754e1769.
ꢂ
€
[42] E. Colacio, J.M. Domínguez-Vera, F. Lloret, J.M.M. Sanchez, R. Kivekas,
€€
A. Rodríguez, R. Sillanpaa, Inorg. Chem. 42 (2003) 4209e4214.
[43] X. He, C.-Z. Lu, C.-D. Wu, L.-J. Chen, Eur. J. Inorg. Chem. (2006) 2491e2503.
[44] J.S. Thayer, R. West, Adv. Organomet. Chem. 5 (1967) 169e224.
[45] J.S. Thayer, D.P. Strommen, J. Organomet. Chem. 5 (1966) 383e387.
[46] G. Pilloni, B. Longato, G. Bandoli, B. Corain, J. Chem. Soc. Dalton Trans. (1997)
819e825.
[47] M. Necas, M. Beran, J.D. Woollins, J. Novosad, Polyhedron 20 (2001) 741e746.
[48] P.C. Ford, E. Cariati, J. Bourassa, Chem. Rev. 99 (1999) 3625e3648.
[49] A. Hiromi, T. Kiyoshi, S. Yoichi, I. Shoji, K. Noboru, Inorg. Chem. 44 (2005)
9667e9675.
Appendix B. Supplementary data
Supplementary data related to this article can be found at http://
dx.doi.org/10.1016/j.jorganchem.2014.09.016.
References
[50] C. Kutal, Coord. Chem. Rev. 99 (1999) 213e252.
[51] W.F. Fu, X. Gan, C.M. Che, Q.Y. Cao, Z.Y. Zhou, N.N.Y. Zhu, Chem. Eur. J. 10
(2004) 2228e2236.
[52] R.D. Pike, K.E. deKrafft, A.N. Ley, T.A. Tronic, Chem. Commun. (2007)
3732e3734.
[53] S. Hu, A.-J. Zhou, Y.-H. Zhang, S. Ding, M.-L. Tong, Cryst. Growth Des. 6 (2006)
2543e2550.
[54] V.W.-W. Yam, K.M.-C. Wong, Chem. Commun. 47 (2011) 11579e11592.
[1] K.-S. Gan, T.S.A. Hor, in: A. Togni, T. Hayashi (Eds.), Ferrocenes: Homogeneous
Catalysis, Organic Synthesis, Materials Science, VCH, New York, 1995, pp.
3e104.
[2] T. Hayashi, in: A. Togni, T. Hayashi (Eds.), Ferrocenes: Homogeneous Catalysis,
Organic Synthesis, Materials Science, VCH, New York, 1995, pp. 105e142.
ꢀ
ꢁ
ꢂ
[3] S.W. Chien, T.S.A. Hor, in: P. Stepnicka (Ed.), Ferrocenes: Ligands, Materials
and Biomolecules, John Wiley & Sons, Ltd., West Sussex, 2008, pp. 33e116.
ꢀ
ꢁ
ꢂ
[4] T.J. Colacot, S. Parisel, in: P. Stepnicka (Ed.), Ferrocenes: Ligands, Materials and
Biomolecules, John Wiley & Sons, Ltd., West Sussex, 2008, pp. 117e140.
[5] D.J. Young, S.W. Chien, T.S.A. Hor, Dalton Trans. 41 (2012) 12655e12665.
[6] G. Bandoli, A. Dolmella, Coord. Chem. Rev. 209 (2000) 161e196.
[55] D. Li, Y.-F. Luo, T. Wu, S.W. Ng, Acta Crystallogr. Sect.
E 60 (2004)
m927em929.
[56] S.P. Neo, Z.-Y. Zhou, T.C.W. Mak, T.S.A. Hor, J. Chem. Soc. Dalton Trans. (1994)
3451e3458.
[57] J. Díez, M.P. Gamasa, J. Gimeno, M. Lanfranchi, A. Tiripicchio, J. Organomet.
Chem. 637e639 (2001) 677e682.
ꢂ
[7] R.G. Arrayas, J. Adrio, J.C. Carretero, Angew. Chem. Int. Ed. 45 (2006)
7674e7715.
[8] T.J. Colacot, Chem. Rev. 103 (2003) 3101e3118.
[58] G.A. Bowmaker, C.D. Nicola, Effendy, J.V. Hanna, P.C. Healy, S.P. King,
F. Marchetti, C. Pettinari, W.T. Robinson, B.W. Skelton, A.N. Sobolev,
[9] R.C.J. Atkinson, V.C. Gibson, N.J. Long, Chem. Soc. Rev. 33 (2004) 313e328.
[10] A. Fihri, P. Meunier, J.-C. Hierso, Coord. Chem. Rev. 251 (2007) 2017e2055.
[11] Z. Csok, O. Vechorkin, S.B. Harkins, R. Scopelliti, X. Hu, J. Am. Chem. Soc. 130
(2008) 8156e8157.
[12] S. Jamali, S.M. Nabavizadeh, M. Rashidi, Inorg. Chem. 47 (2008) 5441e5452.
[13] A. Serra-Muns, A. Jutand, M. Moreno-Manas, R. Pleixats, Organometallics 27
(2008) 2421e2427.
[14] R. Kuwano, H. Kusano, Org. Lett. 10 (2008) 1979e1982.
[15] G.D. Vo, J.F. Hartwig, Angew. Chem. Int. Ed. 47 (2008) 2127e2130.
[16] M. Kawatsura, T. Hirakawa, T. Tanaka, D. Ikeda, S. Hayase, T. Itoh, Tetrahedron
Lett. 49 (2008) 2450e2453.
[17] A.P. Shaw, H. Guan, J.R. Norton, J. Organomet. Chem. 693 (2008) 1382e1388.
[18] L.-C. Song, H.-T. Wang, J.-H. Ge, S.-Z. Mei, J. Gao, L.-X. Wang, B. Gai, L.-Q. Zhao,
J. Yan, Y.-Z. Wang, Organometallics 27 (2008) 1409e1416.
[19] N. Fey, J.N. Harvey, G.C. Lloyd-Jones, P. Murray, A.G. Orpen, R. Osborne,
M. Purdie, Organometallics 27 (2008) 1372e1383.
ꢃ
ꢃ
A. Tabacarub, A.H. White, Dalton Trans. 42 (2013) 277e291.
[59] A.L. Boyes, I.R. Butler, S.C. Quayle, Tetrahedron Lett. 39 (1998) 7763e7766.
[60] L.E. Hagopian, A.N. Campbell, J.A. Golen, A.L. Rheingold, C. Nataro,
J. Organomet. Chem. 691 (2006) 4890e4900.
[61] G.A. Grasa, T.J. Colacot, Org. Lett. 9 (2007) 5489e5492.
[62] C. Bianchini, A. Meli, W. Oberhauser, S. Parisel, E. Passaglia, F. Ciardelli,
O.V. Gusev, A.M. Kal'sin, N.V. Vologdin, Organometallics 24 (2005)
1018e1030.
[63] O.V. Gusev, T.A. Peganova, A.M. Kalsin, N.V. Vologdin, P.V. Petrovskii,
K.A. Lyssenko, A.V. Tsvetkov, I.P. Beletskaya, Organometallics 25 (2006)
2750e2760.
[64] C. Nataro, A.N. Campbell, M.A. Ferguson, C.D. Incarvito, A.L. Rheingold,
J. Organomet. Chem. 673 (2003) 47e55.
[65] G. Pilioni, B. Longato, G. Bandoli, Inorg. Chim. Acta 277 (1988) 163e170.
[66] B.D. Swartz, C. Nataro, Organometallics 24 (2005) 2447e2451.
[67] J.E. Aguado, S. Canales, M.C. Gimeno, P.G. Jones, A. Laguna, M.D. Villacampaa,
Dalton Trans. (2005) 3005e3015.
[20] T. Dahl, C.W. Tornoee, B. Bang-Andersen, P. Nielsen, M. Joergensen, Angew.
Chem. Int. Ed. 47 (2008) 1726e1728.
[21] B.-T. Guan, S.-K. Xiang, B.-Q. Wang, Z.-P. Sun, Y. Wang, K.-Q. Zhao, Z.-J. Shi,
J. Am. Chem. Soc. 130 (2008) 3268e3269.
[22] T. Jensen, H. Pedersen, B. Bang-Andersen, R. Madsen, M. Joergensen, Angew.
Chem. Int. Ed. 47 (2008) 888e890.
[68] Z.-G. Fang, T.S.A. Hor, Y.-S. Wen, L.-K. Liu, T.C.W. Mak, Polyhedron 14 (1995)
2403e2409.
[69] T.S.A. Hor, L.-T. Phang, L.-K. Liu, Y.-S. Wen, J. Organomet. Chem. 397 (1990)
29e36.
[23] J. Arias, M. Bardaji, P. Espinet, Inorg. Chem. 47 (2008) 1597e1606.
[24] K.M. Clapham, A.S. Batsanov, R.D.R. Greenwood, M.R. Bryce, A.E. Smith,
B. Tarbit, J. Org. Chem. 73 (2008) 2176e2181.
[25] M. Trivedi, R. Nagarajan, A. Kumar, N.P. Rath, P. Valerga, Inorg. Chim. Acta 376
(2011) 549e556.
[26] M. Trivedi, G. Singh, A. Kumar, N.P. Rath, Dalton Trans. 42 (2013)
12849e12852.
[27] M. Trivedi, Bhaskaran, G. Singh, A. Kumar, N.P. Rath, J. Organomet. Chem. 758
(2014) 9e18.
[70] D.T. Hill, G.R. Girard, F.L. McCabe, R.K. Johnson, P.D. Stupik, J.H. Zhang,
W.M. Reiff, Eggleston, Inorg. Chem. 28 (1989) 3529e3533.
[71] B.S. Furniss, A.J. Hannaford, V. Rogers, P.W.G. Smith, A.R. Tatchell, Vogel,s
Textbook of Practical Organic Chemistry, fourth ed., Longman, London, 1978.
[72] G.M. Sheldrick, Acta Crystallogr. Sect. A 64 (2008) 112e122.
[73] G.M. Sheldrick, SHELX-97; Programme for Refinement of Crystal Structures,
University of Gottingen, Gottingen, Germany, 1997.
[74] PLATON A.L. Spek, Acta Crystallogr. 46A (1990) C34.