The preparation and characterisation of rhodium(III) and Iridium(III) half sandwich complexes with napthalene-1,8-dithiolate, acenaphthene-5,6-dithiolate and biphenyl-2,2′-dithiolate

Article abstract of DOI:10.1016/j.jorganchem.2014.10.023

The synthesis of rhodium(III) and iridium (III) half sandwich complexes [Cp?M(PEt₃) (S-R-S)], M = Rh, Ir; S-R-S = naphthalene-1,8-dithiolate (NaphthS₂, a), acenaphthene-5,6-dithiolate (AcenapS₂, b) and biphenyl-2,2′-dithiolate (BiphenS₂, c) is reported. We also describe the isolation of a new compound acenaphthene-1,8-dithiol. All complexes have been fully characterised using multinuclear NMR spectroscopy and single crystal X-ray diffraction. The ligands naphthalene-1,8-dithiol (H₂a), acenaphthene-1,8-dithiol (H₂b), 1,1′-biphenyl-2,2′-dithiol (H₂c) and benzene-1,2-dithiol (H₂d) have also been characterised by single crystal X-ray diffraction.

Full text of DOI:10.1016/j.jorganchem.2014.10.023

Journal of Organometallic Chemistry 776 (2015) 7e16
Contents lists available at ScienceDirect
Journal of Organometallic Chemistry
journal homepage: www.elsevier.com/locate/jorganchem
The preparation and characterisation of rhodium(III) and Iridium(III)
half sandwich complexes with napthalene-1,8-dithiolate,
0
acenaphthene-5,6-dithiolate and biphenyl-2,2 -dithiolate
Phillip S. Nejman, Brian Morton-Fernandez, Nicholas Black, David B. Cordes,
*
Alexandra M.Z. Slawin, Petr Kilian, J. Derek Woollins
EASTChem ESchool of Chemistry, University of St Andrews, St Andrews, Fife KY16 9ST, UK
a r t i c l e i n f o
a b s t r a c t
Article history:
Received 27 August 2014
Received in revised form
The synthesis of rhodium(III) and iridium (III) half sandwich complexes [Cp*M(PEt ) (S-R-S)], M ¼ Rh, Ir;
3
S-R-S ¼ naphthalene-1,8-dithiolate (NaphthS
2 2
, a), acenaphthene-5,6-dithiolate (AcenapS , b) and
0
biphenyl-2,2 -dithiolate (BiphenS
2
, c) is reported. We also describe the isolation of a new compound
10 October 2014
acenaphthene-1,8-dithiol. All complexes have been fully characterised using multinuclear NMR spec-
troscopy and single crystal X-ray diffraction. The ligands naphthalene-1,8-dithiol (H a), acenaphthene-
d) have also been charac-
Accepted 16 October 2014
Available online 31 October 2014
2
0 0
2 2 2
b), 1,1 -biphenyl-2,2 -dithiol (H c) and benzene-1,2-dithiol (H
1,8-dithiol (H
terised by single crystal X-ray diffraction.
Keywords:
Sulfur
©
2014 Elsevier B.V. All rights reserved.
Bidentate
Iridium
Rhodium
Half sandwich
Phosphine
Introduction
More recently there has been an interest in using naphthalene-
0 0
,8- and 1,1 -biphenyl-2,2 - dithiolate based ligands bound to iron
1
The coordination of S,S bidentate ligands remains an important
area of chemistry. Complexes bearing this type of ligand have a
number of industrial applications including vulcanisation [1e4],
lubricant additives [5] and catalysis [1e4]. In addition S,S donors
can support unusual magnetic properties and are important in
biological systems [6]. As part of our interest in the properties of
sulfur donor systems we have investigated a series of dithiolate
ligands bound to aromatic backbones.
There has been little study on the coordination chemistry of
these types of ligands thus far. One exception to this is the work by
Teo and co-workers carried out in the late 1970s and early 1980s on
the oxidative addition of tetrathionaphthalene (TTN), tetra-
chlorotetrathionaphthalene (TCTTN) and tetrathiotetracene (TTT)
to a variety of low valent metal substrates (Fig. 1) [7e14]. Another
as electron transfer catalysts designed to mimic iron hydrogenases
(Fig. 2) [16e21]. The structurally related compound acenaph-
thene-5,6-dithiolate is less well documented with only one
example of complexes incorporating this type of ligand out with
our research [22]. Topf and co-workers have used the acenaph-
thene backbone as a linker between a 1,2-diimine unit and a
dithiolate binding site. The iron carbonyl complex bearing this
ligand was shown to have potential as a multielectron transfer
photosensitiser for artificial photosynthesis and as a bio-inspired
photoredox catalyst [22].
With the exception of the electron transfer mimics the coordi-
0
0
nation chemistry of 1,1 -biphenyl-2,2 dithiolate has seen little
investigation. Two molybdenum based complexes have been syn-
thesised with one bearing an Mo oxygen triple bond [23,24]. A
derivatised version of the ligand has been bound to copper [25]
with mono- and dinuclear nickel complexes also reported [26].
There has also been two reports on methods to synthesise titano-
interesting
chlorodithionaphthalene (HCDTN) resulted in an unusual trinu-
clear nickel complex [Ni (PPh (S ] with the HCDNT acting
as a bridging ligand [15].
system
bearing
the
related
hexa-
3
3
)
3
2 6 3
C10Cl )
0
cene-2,2 -dithiolatobiphenyl [27,28].
Herein we describe the synthesis of a series of dithiolato com-
plexes bound to rhodium(III) and iridium(III) metal centres. We also
report the isolation of a new dithiol, acenaphthene-1,8-dithiol,
*
Corresponding author.
E-mail address: jdw3@st-and.ac.uk (J.D. Woollins).
0
along with crystallographic studies of naphthalene-1,8-dithiol, 1,1 -
http://dx.doi.org/10.1016/j.jorganchem.2014.10.023
022-328X/© 2014 Elsevier B.V. All rights reserved.
0

8
P.S. Nejman et al. / Journal of Organometallic Chemistry 776 (2015) 7e16
Fig. 1. Structurally related aromatic sulfur donating ligands.
0
biphenyl-2,2 -dithiol and benzene-1,2-dithiol. All new complexes
and the new dithiol have been fully characterised principally by
multinuclear NMR spectroscopy, elemental analysis and single
crystal X-ray diffraction.
Results and discussion
The diprotic pro-ligands naphthalene-1,8-dithiol [Naphth(SH)
2
]
0
(H
2
a), acenaphthene-5,6-dithiol [Acenap(SH)
2
] (H
2
b) and 1,1 -
0
biphenyl-2,2 -dithiol [Biphen(SH)
2
] (H
2
c) were synthesised from
their respective disulfides naphtho [1,8-cd]-1,2-dithiole [29], 5,6-
dihydroacenaphtho [5,6-cd]-1,2-dithiole [30] and dibenzo [c,e]-
1
,2-dithiin [31] (Scheme 1). Reduction of the disulfides was per-
formed using NaBH [32], which was followed by an acidic workup
after which all three pro-ligands were isolated as colourless solids,
each possessing only a mild thiol odour. Benzene-1,2-dithiol (H d)
4
2
was prepared according to the literature and purified by distillation
to afford a colourless liquid with a strong thiol odour (Scheme 1)
[
33]. H
acterised earlier [31,32,34], for completeness we report their X-ray
structures here. In contrast, H b was not isolated previously, and
2 2 2
a, H c and H d were isolated and spectroscopically char-
2
we report full spectral characterisation as well as its X-ray
structure.
2 2
Acenap(SH) (H b) was isolated as a pale brown solid, and was
1
13
1
fully characterised by H, C{ H} NMR spectroscopy, ES-MS, IR,
Raman and X-ray crystallography. The compound was found to be air
stable with no decomposition observed over several months whilst
storing in air. For our purposes the compound didn't require further
purification, however analytically pure colourless crystalline mate-
rial was obtained after recrystallization from boiling hexane; the
ꢁ
2 2 4
Scheme 1. Synthesis of pro-ligands H aeH d. Conditions: i) 1. NaBH , EtOH/THF, 0 C.
2
1
homogeneity was verified by microanalysis. The H NMR spectrum
ꢁ
. HCl(aq). ii) 1. n-BuLi, TMEDA, hexane, 0 C. 2. S
8
, ꢀ20 ꢁC. 3. HCl(aq).
of H
the aromatic protons as a set of partially overlapping doublets cen-
tred at
¼ 7.47 and 7.09 ppm, while the signal from the alkyl bridge
can be seen as a broad singlet at
spectrum showed the expected signals including all the quaternary
2 3
b (in CDCl ) shows the distinctive thiol peak at
d
¼ 4.16 ppm and
ꢀ
d
correspond to
n
(SeH) vibrations. The mass spectrum (ES ) shows
13
1
þ
d
¼ 3.31 ppm. The C{ H} NMR
the parent ion at m/z 217 corresponding to the loss of H .
Starting dichloro complexes [Cp*RhCl
2 3 2-
PEt ] (1) and [Cp*IrCl
ꢀ1
carbons. A medium intensity band at 2546 cm in the Raman
PEt ] (2) were prepared according to literature procedures [35,36].
3
ꢀ1
31
1
spectrum and a weak band at 2510 cm
in the IR spectrum
The P{ H} NMR spectra of 1 and 2 showed peaks at
and
coupling of 138 Hz observed for 1 (Table 1). For completeness, we
report X-ray crystal structures of 1 and 2 as these were not reported
previously.
d
¼ 28.2 ppm
1
d
¼ ꢀ5.8 ppm respectively with the corresponding
J
PRh
Table 1
31
1
P{ H} NMR data (CDCl
3
) for complexes 1, 2, 3aec and 4aec. All
d
values are in ppm
and J values in hertz.
1
3a
24.6
146.7
4a
3b
24.9
145.9
4b
3c
d
P
28.2
137.5
2
21.9
150.8
4c
1
J
PRh
d
P
ꢀ5.8
ꢀ13.9
ꢀ14.4
ꢀ15.5
Fig. 2. An iron dithiolato complex active in electron transfer processes.

P.S. Nejman et al. / Journal of Organometallic Chemistry 776 (2015) 7e16
9
Scheme 2. General reaction conditions for the synthesis of 3aec and 4aec.
The synthesis of [Cp*Rh(NaphthS
PEt ] (3b), [Cp*Rh(BiphenS )PEt ] (3c), [Cp*Ir(NaphthS
Cp*Ir(AcenapS )PEt ] (4b) and [Cp*Ir(BiphenS )PEt
3
2
)PEt
3
] (3a), [Cp*Rh(AcenapS
)PEt ] (4a),
] (4c) are
2
)
Interestingly, the two CH
2
hydrogen atoms in 3c are anisochronous,
3
2
3
2
3
displaying two distinct complex multiplets [2.04e1.86 (m, 3H) and
1.73e1.58 (m, 3H)]. This is likely to be the result of the restricted
rotation or arylearyl bond in the biphenyldithiolate ligand, which
introduces an axis of chirality, thus making the two CH
3c diastereotopic. As expected, the C{ H} NMR spectra displays
[
2
3
2
shown in Scheme 2. The metathesis of the chloride ligands with the
dithiol ligands proceeds smoothly in refluxing THF. The presence of
the phosphine group allowed for easy monitoring of the progress of
the reaction by 31P NMR spectroscopy. When first mixed a cloudy
solution forms which after refluxing becomes clear. The reaction
proceeds with loss of hydrogen chloride; despite no trapping agent
being used good isolated yields were obtained (75e83% after pu-
rification). In all cases purification was performed by column
2
protons in
13
1
only one signal corresponding to the ethyl CH
2
carbons in each of
þ
þ
the complexes 3aec. The mass spectra (ES for 3aeb, APCI for 3c)
þ
show the [M þ H ] ions at m/z 547, 573 and 573, respectively. Purity
of the new complexes 3aec was verified by microanalysis.
31
1
The P{ H} NMR spectra (CDCl
3
) of complexes 4aec (Table 1)
chromatography on silica using dichloromethane as the eluent.
also exhibit an upfield shift compared to the starting complex 2
The 31P{ H} NMR data (CDCl
1
) for complexes 1, 2, 3aec and
(
Dd ¼ 8.1e9.7 ppm). While the upfield shift in the iridium series is
3
4
aec are shown in Table 1. For complexes 3aec there is a slight
slightly larger compared to that of the rhodium analogues, less
variation is observed between the complexes 4aec. The H NMR
31
1
upfield shift in the P NMR spectra compared to the starting
complex 1 (Dd ¼ 3.3e6.3 ppm), the coordination of the dithiolate
spectra of 4aec (CDCl3) show the same pattern as the rhodium
analogues, including the anisochronicity of the CH (ethyl) hydro-
2
1
ligand is also accompanied by a small increase in the JRhP coupling
in 3aec compare to 1.
gens in 4c [
d
H
2.05e1.87 (m, 3H), 1.73e1.56 (m, 3H)] (see above for
1
þ
The H NMR spectra (CDCl
3
) of 3aec show the aromatic ligand
discussion of the same feature in 3c). The mass spectra (ES for 4a
5
þ
þ
backbone signals in the range of 7.86e6.68 ppm. The
nals (1.52e1.45 ppm, CH groups) are split into doublets by the long
range phosphorus coupling ( JHP ¼ 2.7e2.9 Hz). The ethyl groups
show multiplets for the CH groups and doublet of triplets for the
CH HH ¼ 7.8 Hz).
groups in 3a and 3b ( JHP ¼ 15.8 Hz,
h
eCp* sig-
and 4b, APCI for 4c) show the [M þ H ] ions at m/z 637, 663, 663
3
respectively. Peaks corresponding to the loss of PEt group are also
3
4
observed and in the case of 4a and 4b these are base peaks. Once
again the IR and Raman spectra showed the expected bands and
excellent microanalysis data were obtained for 4aec.
2
3
3
3
J
Scheme 3. Reaction conditions for the synthesis of 3d and 4d.

10
P.S. Nejman et al. / Journal of Organometallic Chemistry 776 (2015) 7e16
Fig. 3. Displacement ellipsoid representation of H
one of the four independent molecules is drawn for H
2
a (Top left), H
c.
2 2 2
b (Top right), H c (Bottom left) and H d (Bottom right). Carbon-bound hydrogen atoms are omitted for clarity, only
2
Interestingly in contrast to the above examples, the reaction
between benzene-1,2-dithiol and complexes 1 and 2 resulted in 3d
and 4d (Scheme 3) that have been previously reported by Xi and co-
workers [37]. This was confirmed by H and C NMR spectroscopy
in addition to elemental analysis. We have no ready explanation for
this difference in reactivity.
The torsion angle S(1)eC(1)/C(9)eS(9) has increased in both
ꢁ ꢁ
H a and H b by 5.2e6.1 and 1.1e2.6 respectively compared to
2 2
their corresponding disulfides, indicating a mild but noticeable out
1
13
of plane displacement. The torsion angle between the phenyl rings
ꢁ
ꢁ
ꢁ
in H
2
c varies at ꢀ79.8 , ꢀ82.7 and ꢀ102.1 , which suggests the
ꢁ
ideal position for the rings to sit is approximately 10e12 off
perpendicular.
Although synthesis and spectral characterisation of complexes 1
and 2 were previously reported [35], no x-ray crystal data was
published. Crystals suitable for X-ray studies were obtained from
diethylether by slow evaporation.
The X-ray diffraction of 1 and 2 (Fig. 4, Table 4) shows that the
complexes are isostructural, attaining piano stool geometry with a
X-ray crystallography
Pro-ligands H
Despite H
2
aed and dichloro complexes 1 and 2
2
a/c/d being reported and spectroscopically charac-
terised previously no X-ray crystal data has been published. The
solid state structures of the pro-ligands H aeH d are shown in
Fig. 3, with selected structural parameters of H a/b in Table 2 and
c/d in Table 3. There are two molecules within the asymmetric
unit for H a/b/d with four present in H c. When compared to the
respective disulfide, the S$$$S distances have increased by ca.
.0e1.2 Å in H a/b as the bonding interaction is replaced by a
2
2
2
H
2
Table 2
2
2
ꢁ
Selected bond lengths [Å], angles [ ] and displacements [Å] for H
2
a and H
2
b.
H
2
a
2
H b
1
2
repulsive one [38,39]. These observations are confirmed by the
splay angles, with the dithiols having a positive values of 10.4(9)e
S(1)eC(1)
S(9)eC(9)
S(1)/S(9)
C: (1)e(10)e(5)e(6)
C: (9)e(10)e(5)e(4)
S(1)eC(1)/C(10)eS(9)
Splay angle
1.788(3) [1.786(5)]
1.784(3) [1.786(5)]
2.951(2) [2.919(2)]
176.8(3) [176.9(4)]
178.3(3) [178.4(4)]
5.4(2) [6.3(2)]
1.785(4) [1.782(4)]
1.788(4) [1.788(4)]
3.104(1) [3.264(2)]
178.9(3) [179.4(3)]
178.0(3) [177.0(3)]
3.0(2) [1.5(2)]
ꢁ
ꢁ
1
1.8(9) and 15.9(9)e20.5(9) in
compared to negative values in their corresponding disulfides. The
increase in the S/S distance is larger in H c (1.65e2.67 Å) as the
rotation around the arylearyl bond allows the sulfur atoms to lie
further apart. Interestingly the S/S distance (3.068(1) Å) in H d is
2 2
H a and H b respectively
2
11.8(9) [10.4(9)]
15.9(9) [20.5(9)]
2
Out of plane displacement
between that seen in the other two planar ligands despite being
ortho substituted. The splay angle has a small negative value
indicating a slight attractive force between the two sulfur atoms.
S(1)
S(9)
0.092 [0.152]
0.146 [0.147]
0.099 [0.018]
0.063 [0.103]
[] denotes data from second molecule in asymmetric unit.

P.S. Nejman et al. / Journal of Organometallic Chemistry 776 (2015) 7e16
11
Table 3
Selected bond lengths [Å], angles [ ] and displacements [Å] for H
Table 4
ꢁ
ꢁ
2
c and H
2
d.
Selected bond lengths [Å] and angles [ ] for 1 & 2.
H
2
ca
H
2
d
1
2
S(1)eC(1)
S(8)eC(8)
S(1)/S(8)
1.764(8)e1.783(8)
1.760(8)e1.785(8)
3.716e4.335(3)
S(1)eC(1)
S(2)eC(2)
S(1)/S(2)
1.776(4) [1.773(3)]
1.771(3) [1.777(4)]
3.068(1) [3.072(1)]
M(1)eCl(1)
M(1)eCl(2)
M(1)eP(1)
M(1)eC(1)
M(1)eC(2)
M(1)eC(3)
M(1)eC(4)
M(1)eC(5)
2.4124(8)
2.4072(7)
2.3102(7)
2.155(3)
2.222(3)
2.230(3)
2.155(3)
2.175(3)
90.95(3)
89.63(3)
89.33(2)
2.425(1)
2.423(1)
2.320(1)
2.182(5)
2.255(5)
2.255(5)
2.172(5)
2.177(5)
88.36(4)
89.41(4)
89.10(4)
C: (1)e(2)e (ꢀ)79.8e(ꢀ)102.1(9) S(1)eC(1)/C(2)eS(2) 1.1(4) [2.3(4)]
(
7)e(8)
Splay angleb
ꢀ3.4(4) [ꢀ3.5(4)]
Out of plane displacement
S(1)
S(8)
0.007e0.065
0.012e0.137
S(1)
S(2)
0.025 [0.041]
0.030 [0.036]
Cl(1)eM(1)eCl(2)
Cl(1)eM(1)eP(1)
Cl(2)eM(1)eP(1)
[
] denotes data from second molecule in asymmetric unit.
a
Ranges quoted for molecules within the asymmetric unit.
Calculated as (S(1)eC(1)eC(2) þ C(1)eC(2)eS(2)) e 240.
b
3
.173(1) Å for H
2
a and 3.1038(13) Å to 3.231(2) Å for H
2
b as the
slightly tilted h5eCp* ring (RheC bond lengths 2.155(3)e
rhodium centre bridges the peri positions. Complex 3c has the
largest distance between the sulfur atoms (3.448(1) Å) as they are
attached to a much more flexible backbone. This represents a
decrease compared to the pro-ligand as the sulfur atoms are held
closer together within the coordination sphere.
2
.230(3) Å; IreC 2.172(5)e2.255(5) Å). The Cl-M-P angles are all
ꢁ
close to the idealised 90 whilst the RheCl/P bond lengths are
similar to other half sandwich complexes, ranging from 2.322 to
2
.341 Å for the RheP bond and 2.392e2.413 Å for the RheCl bond
All the non-Cp* angles around the rhodium centre are slightly
[40,41]. The IreC/P bond lengths were also comparable to the
ꢁ
reduced to less than 90 for complexes 3aeb. This can be
literature, IreP; 2.284e2.318 Å, IreCl; 2.402e2.418 Å [42].
explained by the rigid ligand backbone preventing the sulfur
atoms from moving further apart to adopt a more relaxed geom-
etry. The effect is most marked for the naphthalene system as the
sulfur atoms in the peri-position are restricted to a slightly shorter
distance than those in the acenaphthene system. The splay angles
Rhodium complexes 3aec
The solid state structures of 3ae3c are shown in Figs. 5 and 6
with selected structural parameters listed in Table 5. As with
complexes 1 and 2, the rhodium centre adopts piano stool ge-
ometry. The RheS bonds lengthen going through the series,
varying from 2.3371(9) and 2.3307(7) Å in 3a, 2.342(2) and
ꢁ
ꢁ
are almost identical at 19.7 (3a) and 20.5 (3b), respectively. Both
of these values are increased compared to the pro-ligands as the
rhodium metal pushes the sulfur atoms apart. The torsion angle
S(1)eC(11)/C(19)eS(19) is slightly bigger in 3a than in 3b, as is
the out of plane displacement of the sulfur atoms from the back-
bone. Both complexes show comparable buckling of the central
ring system with the central CeCeCeC torsions ranging from
2
.344(2) Å in 3b to 2.3840(8) and 2.3821(9) Å in 3c. These are
comparable to other half sandwich complexes with RheS bond
lengths reported by Jin and co-workers ranging from 2.340 to
2
.386 Å [43e45]. The RheP bonds are slightly shortened in all the
ꢁ
ꢁ
complexes, 3a 2.2914(8) Å, 3b, 2.299(2) Å, 3c 2.2939(8) Å
compared to 1. The RheP bond lengths are similar to those pre-
viously reported for half sandwich rhodium complexes with
neutral phosphine ligands ranging from 2.274 to 2.295 Å [46]. The
distance between the two sulfur donor atoms increases through
the series. Comparing the S$$$S distance between the free and
bound ligands an increase is observed from 2.951(2) Å to
176.7 e178.9 .
Complex 3c shows a more relaxed dithiol ligand geometry,
resulting in two of the angles around the rhodium being slightly
ꢁ
ꢁ
ꢁ
above 90 (92.69(3) , 93.16(3) ). The ability of the backbone to twist
along the central CeC bond removes the restrictions on the sulfur
atoms observed in 3a and 3b. The torsion angle between the two
ꢁ
aromatic rings is ꢀ68.0(4) , a smaller value than that observed in
2 3 2 2 2 3 2 2
Fig. 4. Displacement ellipsoid representation of (left to right) [Cp*RhCl PEt ]$H O (1$H O) and [Cp*IrCl PEt ]$½H O (2$1/2H O) showing the piano stool geometry. The water
molecules and hydrogen atoms are omitted for clarity.

12
P.S. Nejman et al. / Journal of Organometallic Chemistry 776 (2015) 7e16
Fig. 5. Displacement ellipsoid representation of (left to right) [Cp*Rh(NaphthS
b for clarity, hydrogen atoms are omitted from all structures for clarity.
2 3 2 3 2 2
)PEt ] (3a) and [Cp*Rh(AcenapS )PEt ] (3b). The molecule of solvated CH Cl has been omitted from
3
the pro-ligand. The out of plane displacement of the sulfur atoms is
smaller than in the peri-backbone containing complexes.
Conclusions
We have prepared and fully characterised a series of new Rh(III)
5
and Ir(III)
h
eCp* half sandwich complexes by ligand replacement
PEt ] and [Cp*IrCl PEt ] with a series of
Iridium complexes 4aec
reactions of [Cp*RhCl
2
3
2
3
The solid state structures of 4aec are shown in Figs. 7 and 8
with selected structural parameters listed in Table 6. The lantha-
nide contraction results in the atomic radius of iridium being
similar to that of rhodium, the complexes adopting similar struc-
tures to that of rhodium analogues. The drop in the observed tilt of
the Cp* moiety is less in this series cf. the rhodium complexes. The
IreS bond lengthens going from 4ae4c ranging from 2.339(1) Å in
dithiols attached to aromatic backbones. This work clearly dem-
onstrates the utility of these sulfur ligands in organometallic
complexes. Further work on the usefulness of the complexes
described here in devices such as solar cells and for the formation of
multimetallic systems will be conducted in the coming months.
Experimental
4
a to 2.409(9) Å in 4c and are comparable to other IreS bonds
[
47]. The IreP bond length increases going from 4a to 4c with all
General
the complexes showing a shortened IreP bond compared to the
starting complex. The S$$$S distance increases across the series as
before.
Unless otherwise stated all manipulations were performed un-
der an oxygen-free nitrogen atmosphere using standard schlenk
techniques and glassware. Solvents were collected from an MBraun
Solvent Purification System or dried and stored according to com-
mon procedures [48]. [Cp*RhCl PEt ] and [Cp*IrCl PEt ] were pre-
2 3 2 3
pared following a procedure similar to that of Maitlis et al. and are
The non-Cp* angles around the iridium centre for 4a and 4b are
ꢁ
ꢁ
ꢁ
all less than 90 , with 4c having two greater than 90 (92.08(3) ,
ꢁ
9
2.64(3) ). The S/S distance, splay angle and torsion S(1)eC(11)/
C(19)eS(19) all increase in the iridium complexes compared to
their rhodium analogues. The out of plane displacement of the
sulfur atoms from the central ring systems are comparable to the
rhodium analogues.
described below [36]. The disulfide precursors were made ac-
cording to literature methods [29e31]. [Naphth(SH)
2
], [Ace-
nap(SH) ] and [Biphen(SH) ] were prepared following a modified
2
2
literature procedure [32]. Benzene-1,2-dithiol was prepared
Table 5
ꢁ
Selected bond lengths [Å], angles [ ] and displacements [Å] for 3aꢀc.
3a
3b
3c
Rh(1)eS(1)
Rh(1)eS(19)
Rh(1)eP(1)
S(1)eC(11)
S(19)eC(19)
S(1)$$$S(19)
2.3371(9) 2.342(2) Rh(1)eS(11)
2.3307(7) 2.344(2) Rh(1)eS(17)
2.2914(8) 2.299(2) Rh(1)eP(1)
1.765(3) 1.764(8) S(11)eC(11)
1.763(3) 1.769(8) S(17)eC(17)
3.173(1) 3.231(2) S(11)/S(17)
2.3840(8)
2.3821(9)
2.2939(8)
1.772(3)
1.790(3)
3.448(1)
92.69(3)
93.16(3)
89.60(3)
S(1)eRh(1)eS(19) 85.64(3) 87.19(6) S(11)eRh(1)eS(17)
S(1)eRh(1)eP(1) 89.40(3) 88.72(7) S(11)eRh(1)eP(1)
S(19)eRh(1)eP(1) 88.33(3) 88.18(7) S(17)eRh(1)eP(1)
Splay angle
19.7
6.63(2)
20.5
4.12(5)
C: (11)e(12)e(18)e(17) ꢀ68.0(4)
S(1)eC(11)/
C(19)eS(19)
C: (11)e(20)e
177.70(3) 176.72(8)
178.10(3) 178.99(8)
(
15)e(16)
C: (19)e(20)e
15)e(14)
(
Out of plane displacement
S(1)
S(19)
0.211
0.067
0.181
0.028
S(11)
S(17)
0.114
0.002
2 3
Fig. 6. Displacement ellipsoid representation of [Cp*Rh(BiphenS )PEt ] (3c). Hydrogen
atoms are omitted for clarity.

P.S. Nejman et al. / Journal of Organometallic Chemistry 776 (2015) 7e16
13
2 3 2 3
Fig. 7. Displacement ellipsoid representation of (left to right) [Cp*Ir(NaphthS )PEt ] (4a), [Cp*Ir(AcenapS )PEt ] (4b). Hydrogen atoms are omitted for clarity.
according to literature [33,34]. The synthesis of [Acenap(SH)
2
] is
calcd. for C16
C, 44.89; H, 7.20. H NMR (500 MHz, CDCl
H30Cl
2
PRh (426.05 g molꢀ1): C, 44.98; H, 7.07. Found:
1
described below. IR and Raman spectra were collected on a Perkin
Elmer 2000 NIR/Raman Fourier Transform spectrometer with a
3
):
d
¼ 2.11e2.03 (m, 6H,
), 1.15 (dt,
). C{ H} NMR (125 MHz,
¼ 98.0 (dd, JCRh ¼ 7.5 Hz, JCP ¼ 2.8 Hz, C , Cp*C), 16.8 (d,
4
PCH
2
CH
3
), 1.66 (d,
J
HP
¼
3.1 Hz, 15H, Cp-CH
3
1
13
1
3
3
13
1
dipole pumped NdYAG near-IR excitation laser. H and C{ H} NMR
spectra were obtained on either a Bruker Avance 300 or a Bruker
J
HP ¼ 15.3 Hz, JHH ¼ 7.8 Hz, 9H, PCH
2 3
CH
1
2
CDCl
3
)
d
q
1
2
Avance III 500 spectrometer with
solvent peaks (CDCl 7.26, 77.2 ppm). P NMR spectra were
performed on a Bruker Avance 300 spectrometer with
external 85% H PO
d
H
&
d
C
relative to TMS or residual
J
CP ¼ 27.3 Hz, PCH
2
CH
3
), 9.3 (Cp-CH
):
3
), 8.0 (d,
J
CP ¼ 4.6 Hz,
31
31
1
1
3
d
H
d
C
PCH
2
CH
3
). P{ H} (121 MHz, CDCl
3
d
¼ 28.17 (d, JPRh ¼ 137.5 Hz).
þ
þ
þ
þ
d
P
relative to
MS (ES ): m/z (%) 391.08 (100) [M ꢀ Cl] . HRMS (ES ) [M ꢀ Cl]
30ClPRh requires 391.0828, found 391.0813.
ꢁ
3
4
. All measurements were performed at 25
C
16
C H
þ/ꢀ
with shifts reported in ppm. Electrospray (ES ) mass spectra were
carried out by the University of St Andrews Mass Spectrometry
þ
2 3
[Cp*IrCl PEt ] (2)
Service and Atmospheric Pressure Chemical Ionisation (APCI ) by
This was prepared as per complex 1 using [Cp*IrCl
.94 mmol) and PEt
2
]
2
(750 mg,
the EPSRC National Mass Spectrometry Service, Swansea. Elemental
analyses were performed by Stephen Boyer at the London Metro-
politan University.
n
0
3
(245 mg, 2.1 mL, 2.07 mmol, 1 M sol THF)
giving 2 as a yellow solid (968 mg, 1.87 mmol, >99%). Crystals
suitable for X-ray work were obtained from ether. Anal. calcd. for
ꢀ
1
C
5
16
H
30Cl
2
IrP (516.11 g mol ): C, 37.20; H, 5.85. Found: C, 37.09; H,
): CH ),
¼ 2.14e2.06 (m, 6H, PCH
HP ¼ 1.7 Hz, 15H, Cp-CH HP ¼ 15.5 Hz,
). C{ H} NMR (125 MHz, CDCl ):
),
[
Cp*RhCl
Cp*RhCl
followed by PEt
2
PEt
3
] (1)
1
.99. H NMR (500 MHz, CDCl
3
d
2
3
[
2 2
] (750 mg, 1.21 mmol) was added to THF (30 mL)
4
3
n
1.67 (d,
J
3
), 1.11 (dt, J
3
(318 mg, 2.7 mL, 2.66 mmol, 1 M sol THF) and the
3
13
1
J
HH ¼ 7.7 Hz, 9H, PCH
2
CH
3
3
suspension refluxed for 2 h. During this time the solid dissolved to
leave a red solution which was cooled and the solvent removed
under vacuum. Drying under vacuum for 4 h removed excess ligand
to afford the product as a red solid (1.03 g, 2.40 mmol, >99%).
Crystals suitable for X-ray work were obtained from ether. Anal.
2
1
d
¼ 91.2 (d, JCP ¼ 2.6 Hz, C
q
, Cp*C), 16.1 (d, JCP ¼ 36.1 Hz, PCH
2 3
CH
2
31
1
8
.9 (Cp-CH
):
HRMS (ES ) [M ꢀ Cl]
81.1376.
3
), 7.5 (d,
J
CP ¼ 3.96 Hz, PCH
2
CH
3
). P{ H} (121 MHz,
þ
þ
CDCl
3
d
¼ ꢀ5.78 (s). MS (ES ): m/z (%) 481.13 (100) [M ꢀ Cl] .
þ
þ
C
16
H30ClIrP requires 481.1402, found
4
Table 6
ꢁ
Selected bond lengths [Å], angles [ ] and displacements [Å] for 4aec.
4a
4b
4c
Ir(1)eS(1)
Ir(1)eS(19)
Ir(1)eP(1)
S(1)eC(11)
S(19)eC(19)
S(1)/S(19)
S(1)eIr(1)eS(19) 85.60(4)
S(1)eIr(1)eP(1) 89.38(4)
S(19)eIr(1)eP(1) 88.27(4)
2.348(1)
2.339(1)
2.276(1)
1.763(5)
1.765(4)
3.185(2)
2.3509(9) Ir(1)eS(11)
2.3579(9) Ir(1)eS(17)
2.2801(9) Ir(1)eP(1)
2.409(1)
2.4031(9)
2.2993(9)
1.785(4)
1.801(3)
3.463(1)
92.08(3)
92.64(3)
89.45(3)
1.775(3)
1.765(3)
3.262(2)
87.70(3)
88.87(3)
88.23(3)
21.4
S(11)eC(11)
S(17)eC(17)
S(11)/S(17)
S(11)eIr(1)eS(17)
S(11)eIr(1)eP(1)
S(17)eIr(1)eP(1)
C: (11)e(12)e(18)e(17) ꢀ66.83(5)
Splay angle
20.5
6.92(3)
S(1)eC(11)/
C(19)eS(19)
C: (11)e(20)e
4.47(5)
176.64(5) 178.91(3)
179.60(5) 177.41(3)
(
15)e(16)
C: (19)e(20)e
15)e(14)
(
Out of plane displacement
S(1)
S(19)
0.195
0.082
0.073
0.131
S(11)
S(17)
0.124
0.005
2 3
Fig. 8. Displacement ellipsoid representation of [Cp*Ir(BiphenS )PEt ] (4c). Hydrogen
atoms are omitted for clarity.

14
P.S. Nejman et al. / Journal of Organometallic Chemistry 776 (2015) 7e16
[
Acenap(SH)
A solution of [AcenapS
2
] (H
2
b)
[Cp*Rh(BiphenS
This was prepared as per complex 3a using [Cp*RhCl
(150 mg, 0.35 mmol) and [Biphen(SH) ] (122 mg, 0.56 mmol) with
2 3
)PEt ] (3c)
2
] (100 mg, 0.46 mmol) in THF (30 mL)
2 3
PEt ]
was added dropwise to an ethanol (10 mL) suspension of NaBH
(
4
2
ꢁ
80 mg, 2.11 mmol) at 0 C. Upon complete addition the reaction
refluxing for 5 h 3c was obtained as a dark purple solid (160 mg,
was stirred for 15 min at this temperature then water (30 mL)
added. The solution was acidified using 3 M HCl then extracted with
ether (3 ꢂ 30 mL) and the combined organic layers dried over
magnesium sulfate. Removal of the solvent under vacuum yielded a
very pale brown solid (98 mg, 0.45 mmol, 97%). Crystals suitable for
X-ray work were obtained from recrystallising in boiling hexane.
0.27 mmol, 80%). Crystals suitable for X-ray work were obtained
ꢀ
1
from CH
2
Cl
2
. Anal. calcd. for C28
H
38PRhS
2
(572.12 g mol ): C, 58.72;
):
1
H, 6.69. Found: C, 58.69; H, 6.74. H NMR (300 MHz, CDCl
3
d
¼ 7.69e7.61 (m, 2H, AreH), 7.19e7.12 (m, 2H, AreH), 7.01e6.92 (m,
3 4
2H, AreH), 6.69 (dd, JHH ¼ 7.5 Hz, JHH ¼ 1.6 Hz,1H, AreH), 6.68 (dd,
3
4
J
HH ¼ 7.5 Hz, JHH ¼ 1.6 Hz, 1H, AreH), 2.04e1.86 (m, 3H, PCH
2
CH
),1.04
). C{ H} NMR
, AreC), 140.8 (C
, AreC), 137.4 (CH, AreC), 135.5 (CH, AreC), 130.9
(CH, AreC), 130.6 (CH, AreC), 126.1 (CH, AreC), 125.9 (CH, AreC),
125.7 (CH, AreC), 125.3 (CH, AreC), 99.2 (m, C , Cp*C), 16.4 (d,
3
),
ꢀ1
4
Anal. calcd. for C12
C, 65.91; H, 4.75 H NMR (500 MHz, CDCl
H
10
1
S
2
(218.02 g mol ): C, 66.04; H, 4.62. Found:
):
¼ 7.47 (d,
1.73e1.58 (m, 3H, PCH
2
CH
3
),1.52 (d, JHP ¼ 2.9 Hz,15H, Cp-CH
3
3
3
13
1
3
d
(dt,
(125 MHz, CDCl
AreC), 139.1 (C
q
J
HP ¼ 15.0 Hz,
J
HH ¼ 7.6 Hz, 9H, PCH
2 3
CH
3
3
J
HH ¼ 7.2 Hz, 2H, AreH), 7.09 (d, JHH ¼ 7.2 Hz, 2H, AreH), 4.16 (s,
3
):
d
¼ 151.1 (C , AreC), 150.3 (C
q
q
q
,
13
1
2
H, 2 ꢂ SeH), 3.31 (s, 4H, CH
¼ 145.8 (C , AreC), 141.3 (C
, AreC), 120.1 (CH, AreC), 30.0 (CH
max/cm 2921w ( C-H), 2510w ( S-H), 1459s, 1197m, 833s, 810m.
Raman (glass capillary):
2
CH
, AreC), 133.4 (CH, AreC), 130.4 (C
CH ). IR (KBr):
2
). C{ H} NMR (125 MHz, CDCl
3
):
q
,
d
q
q
AreC), 123.2 (C
q
2
2
q
ꢀ1
1
2
n
n
n
J
CP ¼ 27.0 Hz, PCH
2
CH
3
), 8.6 (Cp-CH
3
), 8.1 (d,
J
CP ¼ 3.8 Hz,
21.85 (d,
Ar-H), 2958m (
P-C). Raman (glass
C-H), 1583s, 1477s,
ꢀ
1
31
1
n
max/cm 3059m (
n
Ar-H), 2931m, (
n
C-H),
PCH
2 3
CH ).
P{ H} NMR (121 MHz, CDCl
3
):
d
¼
1
ꢀ1
2
546s (
n
S-H), 2514s (
n
S-H), 1599s, 1566s, 1440s, 1412s, 1336s, 580s
J
PRh ¼ 150.8 Hz). IR (KBr):
n
max/cm 3040w (
n
nC-H),
ꢀ
ꢀ
(n
C-S). MS (ES ): m/z (%) 217.01 (100) [M ꢀ H] .
2906m (
capillary):
1036s, 774s, 612w (
nC-H),1450s,1414m,1034m, 752s, 722m (n
ꢀ
1
n
max/cm 3043m (
nAr-H), 2915s (
n
þ
[
Cp*Rh(NaphthS
A THF (30 mL) solution containing [Cp*RhCl
.35 mmol) and [Naphth(SH) ] (108 mg, 0.56 mmol) was refluxed
2
)PEt
3
] (3a)
nC-S), 359s, 325s. MS (APCI ): m/z (%) 573.12 (70)
þ
þ
þ
2
PEt
3
] (150 mg,
[M þ H] , 455.03 (20) [M ꢀ PEt
3
], 119.09 (100) [PEt
3
þ H] . HRMS
þ
þ
0
2
(APCI ) [M þ H]
28 2
C H39PRhS requires 573.1280, found 573.1277.
for 3 h. The solution was cooled and the solvent removed to afford
the crude product as a red/orange solid. Purification by flash col-
[
Cp*Ir(NaphthS
This was prepared as per complex 3a using [Cp*IrCl
150 mg, 0.29 mmol) and [Naphth(SH) ] (90 mg, 0.46 mmol) with
2 3
)PEt ] (4a)
umn chromatography (silica gel/CH
pound as a red solid (157 mg, 0.28 mmol, 82%). Crystals suitable for
X-ray work were obtained from CH Cl Anal. calcd. for
(546.10 g mol ): C, 57.13; H, 6.64. Found: C, 56.94; H,
2 2
Cl ) yielded the title com-
2
3
PEt ]
(
2
2
2
.
ꢀ
1
refluxing for 4 h 4a was obtained as a yellow solid (138 mg,
0.21 mmol, 75%). Crystals suitable for X-ray work were obtained
C
26
H
36PRhS
2
1
3
6
J
.67. H NMR (300 MHz, CDCl
3
):
d
¼ 7.86 (dd,
J
HH ¼ 7.3 Hz,
ꢀ
1
4
3
4
from CH
2
Cl
2
. Anal. calcd. for C26
H
36IrPS
2
(636.16 g mol ): C, 49.04;
):
¼ 7.83
(d, JHH ¼ 7.3 Hz, 2H, AreH), 7.35 (d, JHH ¼ 7.8 Hz, 2H, AreH), 6.87
HH ¼ 1.2 Hz, 2H, AreH), 7.43 (dd, JHH ¼ 8.0 Hz, JHH ¼ 1.2 Hz, 2H,
1
3
H, 5.70. Found: C, 48.97; H, 5.81. H NMR (300 MHz, CDCl
3
d
AreH), 7.09 (dd,
J
HH ¼ 8.0, 7.3 Hz, 2H, AreH), 2.08e1.95 (m, 6H,
4
3
3
PCH
2
CH
HP ¼ 15.8 Hz, JHH ¼ 7.8 Hz, 9H, PCH
¼ 139.7 (C
CDCl ): , AreC), 136.2 (C
q
28.2 (CH, AreC), 124.7 (CH, AreC), 123.6 (CH, AreC), 99.6 (m, C ,
3
), 1.45 (d,
J
HP
¼
2.7 Hz, 15H, Cp-CH
3
), 1.06 (dt,
). C{ H} NMR (125 MHz,
, AreC), 134.1 (C , AreC),
3
3
3
13
1
(dd, JHH ¼ 7.8, 7.5 Hz, 2H, AreH), 2.09e1.95 (m, 6H, PCH
2
CH
), 0.96 (dt, JHP ¼ 15.9 Hz, JHH ¼ 7.5 Hz,
¼ 137.3 (C
): , AreC),
q q
, AreC), 133.5 (C , AreC), 127.3 (CH, AreC), 124.3 (CH,
3
), 1.43
J
2 3
CH
4
3
3
(
9
d, JHP ¼ 1.8 Hz,15H, Cp-CH
3
3
d
q
q
q
13
1
H, PCH
2
CH
3
). C{ H} NMR (125 MHz, CDCl
3
d
q
1
1
136.5 (C
AreC), 123.8 (CH, AreC), 94.7 (d,
Cp*C), 15.9 (d,
J
CP ¼ 28.1, PCH
2
CH
3
), 8.7 (Cp-CH
). P{ H} NMR (121 MHz, CDCl
3
):
), 7.4 (d,
¼ 24.63
2
2
31
1
J
CP ¼ 2.7 Hz, C
q
, Cp*C), 15.7 (d,
J
CP ¼ 2.9 Hz, PCH
2
CH
3
3
d
1
2
1
ꢀ1
J
CP ¼ 34.9 Hz, PCH
2
CH
3
), 8.3 (Cp-CH
3
), 6.8 (d,
J
CP ¼ 2.7 Hz, CH
3
,
(
d, JPRh ¼ 146.7 Hz). IR (KBr):
n
max/cm 3034w (
n
Ar-H), 2931m (
P-C). Raman (glass
C-H), 1537s, 1314s,
n
C-
31
1
PCH
2
CH
3
). P{ H} NMR (121 MHz, CDCl ):
nAr-H), 2962w (nC-H), 1536s, 1192m, 1032m, 759s,
3
d
¼ ꢀ13.97 (s). IR (KBr):
H
), 1534s, 1192m, 1034m, 883m, 759s, 722m (
n
n
ꢀ1
ꢀ
1
n
max/cm 3034w (
724m ( P-C). Raman (glass capillary):
914s (
capillary):
n
max/cm 3037w (
n
Ar-H), 2912m (
ꢀ
1
þ
þ
n
n
max/cm 3037w (
n
Ar-H),
8
84s, 594w (
n
C-S), 439s. MS (ES ): m/z (%) 547.11 (10) [M þ H] ,
þ
2
n
C-H), 1537s, 1315s, 884s, 787w, 593m (
nC-S), 545m. MS (ES )
4
59.03 (100) [M ꢀ PEt
3
þ OMe], 428.01 (50) [M ꢀ PEt
3
].
þ
m/z (%) 637.17 (10) [M þ H] , 518.07 [M ꢀ PEt
3
].
[
Cp*Rh(AcenapS
This was prepared as per complex 3a using [Cp*RhCl
2
)PEt
3
(3b)
Table 7
2 3
PEt ]
Crystallographic data for complexes 1 and 3aec.
(
150 mg, 0.35 mmol) and [Acenap(SH) ] (122 mg, 0.56 mmol) with
2
1
3a
3b
3c
refluxing for 5 h 3b was obtained as a red solid (166 mg, 0.29 mmol,
8
Anal. calcd. for C28
Empirical
Formula
M
C
16
H
32Cl
2
OPRh
C
26
H
36PRhS
2 29 2 2 28 2
C H40Cl PRhS C H38PRhS
3%). Crystals suitable for X-ray work were obtained from CH
2
Cl
(572.12 g mol ): C, 58.72; H, 6.70.
):
¼ 7.76 (d,
2
.
ꢀ1
H
38PRhS
2
445.21
546.57
657.54
Triclinic
Pꢀ1
572.61
Monoclinic
P2(1)/n
10.5598(11)
19.3610(16)
13.0461(13)
90
95.401(3)
90
2655.4(4)
4
1.432
0.874
21,811
4872
1
Found: C, 58.71; H, 6.92. H NMR (300 MHz, CDCl
3
d
Crystal system Orthorhombic Monoclinic
3
3
J
HH ¼ 6.9 Hz, 2H, AreH), 6.87 (d, JHH ¼ 6.9 Hz, 2H, AreH), 3.13 (s,
Space group
a [Å]
b [Å]
Pbca
P2(1)/n
8.1417(9)
15.5908(18) 9.0275(14)
19.840(3)
90
98.568(7)
90
2490.3(5)
4
1.458
0.928
22,020
4572
0.0272
0.0615
4
4
H, CH
2
CH
2
), 2.09e1.96 (m, 6H, PCH
2
CH
3
), 1.45 (d,
), 1.08 (dt, JHP ¼ 15.4 Hz, JHH ¼ 7.6 Hz, 9H, PCH
C{ H} NMR (125 MHz, CDCl ): , AreC), 141.0 (C
, AreC), 132.4 (C , AreC), 128.7 (CH, AreC), 117.7
Cp*C), 30.0 (CH CH ), 16.14 (d,
), 8.8 (Cp-CH ), 7.5 (d,
J
HP ¼ 2.7 Hz,
17.0730(13)
15.6491(10)
14.2200(10)
90
90
90
3799.3(5)
8
1.557
8.2482(12)
3
3
1
5H, Cp-CH
3
2
CH ).
3
1
3
1
c [Å]
20.787(3)
78.352(8)
78.709(9)
79.883(10)
1471.6(4)
2
1.484
0.976
19,423
5291
0.0817
0.2208
3
d
¼ 141.5 (C
q
q
,
ꢁ
a
b
g
[ ]
AreC), 135.0 (C
q
q
ꢁ
[ ]
ꢁ
(
CH, AreC), 99.4 (m,
C
q
,
2
2
[ ]
1
2
3
V [Å ]
JCP ¼ 28.2 Hz, PCH
2
CH
3
3
J
CP ¼ 2.9 Hz,
24.95 (d,
C-H), 1406s, 1229m,
31
1
Z
r
PCH
2
CH
3
).
P{ H} NMR (121 MHz, CDCl
max/cm 2928s (
104m, 1033s, 831m, 758s, 721s (
3
):
n
d
¼
calcd. [g cm 3
[cm ]
ꢀ
]
1
ꢀ1
JPRh ¼ 145.9 Hz). IR (KBr):
n
ꢀ1
m
1.259
1
n
7
4
n
C-P). Raman (glass capillary):
C-H), 1595s, 1557m, 1406s, 1323s, 1032m, 827m,
Measured refln. 18,532
ꢀ1
max/cm 2910m (
27s ( C-P), 579m (
54.03 (100) [M ꢀ PEt
n
Unique refln.
3474
0.0262
0.0777
þ
þ
R [I > 2
s
(I)]
0.0302
0.1157
n
n
C-S). MS (ES ): m/z (%) 573.13 (35) [M þ H] ,
].
wR
3

P.S. Nejman et al. / Journal of Organometallic Chemistry 776 (2015) 7e16
15
Table 8
0.23 mmol, 80%). Crystals suitable for X-ray work were obtained
Crystallographic data for complexes 2 and 4aec.
ꢀ1
from CH
2
Cl
2
. Anal. calcd. for C28
H
38IrPS
2
(662.17 g mol ): C, 50.80;
1
2
4a
4b
4c
H, 5.78. Found: C, 50.71; H, 5.83. H NMR (300 MHz, CDCl
3
):
d
¼ 7.62
3
4
3
(
dd, JHH ¼ 7.6 Hz, JHH ¼ 1.3 Hz, 1H, AreH), 7.51 (dd, JHH ¼ 7.6 Hz,
Empirical Formula
M
Crystal system
Space group
a [Å]
C
16
H31Cl
2
IrO0.5
P
C
26
H
36IrPS
635.88
Monoclinic Monoclinic Monoclinic
2
C
28
H38IrPS
2
C
28
H
38IrPS
2
4
525.52
Orthorhombic
Pbca
17.174(3)
15.618(2)
14.387(3)
90
661.92
661.92
J
HH ¼ 1.3 Hz, 1H, AreH), 7.13e7.02 (m, 2H, AreH), 6.95e6.88 (m,
3
4
2H, AreH), 6.85 (dd, JHH ¼ 7.5 Hz, JHH ¼ 1.5 Hz, 1H, AreH), 6.73
P2(1)/n
8.1474(11) 8.4020(10)
P2(1)/c
P2(1)/n
10.6306(11)
3
4
(
dd,
PCH
Cp-CH
J
HH ¼ 7.5 Hz,
CH ), 1.73e1.56 (m, 3H, PCH
), 0.95 (dt, JHP ¼ 15.1 Hz, JHH ¼ 7.8 Hz, 9H, PCH
{ H} NMR (125 MHz, CDCl ): , AreC), 150.9 (C
¼ 151.5 (C
139.8 (C , AreC), 137.2 (C , AreC), 137.0 (CH, AreC), 136.1 (CH,
AreC), 131.5 (CH, AreC), 131.0 (CH, AreC), 126.2 (CH, AreC), 125.8
JHH ¼ 1.5 Hz, 1H, AreH), 2.05e1.87 (m, 3H,
4
2
3
2
CH
3
), 1.48 (d, JHP ¼ 1.9 Hz, 15H,
b [Å]
15.543(2)
19.848(4)
90
98.588(8)
90
2485.2(7)
4
1.699
5.631
22,012
4558
0.0255
0.0534
15.6954(17) 19.568(2)
19.852(2)
90
98.810(3)
90
2587.1(5)
4
1.699
5.413
22,582
4744
0.0207
0.0645
3
3
13
3
2
CH
3
).
C
c [Å]
13.1691(13)
90
95.391(7)
90
2727.3(5)
4
1.612
5.135
23,710
4912
0.0222
0.0555
1
ꢁ
a
b
g
[ ]
3
d
q
q
, AreC),
ꢁ
[ ]
90
90
q
q
ꢁ
[ ]
3
V [Å ]
3859.0(10)
8
1.809
7.292
14,170
3482
(
CH, AreC), 125.4 (CH, AreC), 125.3 (CH, AreC), 99.2 (d,
Z
r
2
1
calcd. [g cmꢀ3
J
CP ¼ 2.9 Hz, C
, Cp*C), 16.0 (d, JCP ¼ 34.2 Hz, PCH
2 3
CH ), 8.1 (Cp-
). P{ H} NMR (121 MHz,
]
q
[cm 1
ꢀ
]
2
31
1
m
CH
CDCl
C-H), 2907m (
capillary): max/cm 3043m (
), 7.75 (d,
JCP ¼ 3.8 Hz, PCH
CH
3
3
2
Measured refln.
Unique refln.
R [I > 2
ꢀ1
3
):
d
¼ ꢀ15.53 (s). IR (KBr):
n
max/cm 3040w (
nAr-H), 2958w
(n
n
C-H), 1451s 1034s, 752s, 724m (
n
P-C). Raman (glass
s(I)]
0.0235
0.0627
ꢀ
1
n
n
Ar-H), 2917s (
n
C-H), 1584s, 1479s,
wR
þ
1
6
295s, 1036s, 1006w (
63.18 (100) [M þ H] , 545.09 (55) [M ꢀ PEt
n
P-Ar), 592m (
n
C-S), 362s. MS (APCI ): m/z (%)
þ
3
], 119.09 (80)
þ
þ
þ
C
[PEt
3
þ H] . HRMS (APCI ) [M þ H]
H39IrPS requires 663.1852,
28 2
[
Cp*Ir(AcenapS
This was prepared as per complex 3a using [Cp*IrCl
150 mg, 0.29 mmol) and [Acenap(SH) ] (101 mg, 0.46 mmol) with
2 3
)PEt ] (4b)
found 663.1852.
2 3
PEt ]
(
2
Crystal structure analysis
refluxing for 6 h 4b was obtained as a yellow solid (158 mg,
0
.24 mmol, 83%). Crystals suitable for X-ray work were obtained
ꢀ
1
Data for 2, 3a, 4a and 4c were collected using a Rigaku SCX-Mini
(MoeK, graphite monochromator) at ꢀ100 C; for H b, H d using a
Rigaku FRX (MoeK, confocal optic) equipped with a Dectris P200
detector at ꢀ100 C and for H a, 3b, 3c and 4b using Rigaku FRX
(MoeK, confocal optic) equipped with a Dectris P200 detector
C. Intensities were corrected for Lorentz polarization, and
from CH
2
Cl
2
. Anal. calcd. for C28
H
38IrPS
2
(662.17 g mol ): C, 50.74;
):
1
ꢁ
H, 5.78. Found: C, 50.67; H, 5.89. H NMR (300 MHz, CDCl
d
3
2
2
3
¼ 7.84e7.69 (m, 2H, AreH), 6.81 (d, JHH ¼ 7.2 Hz, 2H, AreH), 3.08
4
ꢁ
(
s, 4H, CH
2
CH
2
), 2.17e2.01 (m, 6H, PCH
), 1.03 (dt, JHP ¼ 16.0 Hz, JHH ¼ 7.6 Hz, 9H, PCH
2
3
CH
3
), 1.50 (d, JHP ¼ 1.9 Hz,
2
3
1
5H, Cp-CH
3
2 3
CH ).
1
3
1
at ꢀ180
ꢁ
C{ H} NMR (125 MHz, CDCl
AreC), 132.8 (C , AreC), 131.7 (C
CH, AreC), 94.5 (d, JCP ¼ 2.5 Hz, C
3
):
d
¼ 141.2 (C
, AreC), 127.7 (CH, AreC), 117.8
, Cp*C), 30.0 (CH CH ), 15.3 (d,
CP ¼ 2.8 Hz,
¼ ꢀ14.37 (s). IR (KBr):
C-H), 1407s, 1031s, 760s, 724s ( C-P), 499m.
C-H), 1595s, 1406s,
q q
, AreC), 141.0 (C ,
absorption. Structures were solved by direct methods and refined
q
q
2
2
by full-matrix least-squares against F (SHELXL) [49]. Hydrogen
(
q
2
J
2
1
2
atoms were assigned riding isotropic displacement parameters and
constrained to idealised geometries.
Non-hydrogen atoms were refined anisotropically. Hydrogen
atoms on carbon atoms were refined using the riding model. In the
J
CP ¼ 35.5 Hz, PCH
2
CH
3
), 8.3 (Cp-CH
3
), 6.9 (d,
):
3
1
1
PCH
2
CH
3
). P{ H} NMR (121 MHz, CDCl
3
d
ꢀ1
n
max/cm
2928s (
n
n
ꢀ
1
Raman (glass capillary):
n
max/cm
C-S), 412s, 373s, 177s. MS (ES ): m/z (%)
].
2910s (n
þ
structure of H c one of the four independent molecules is highly
1323s, 727s (
n
C-P), 579m (
n
2
þ
disordered. Numerous crystallisations were attempted without
success. We were unable to successfully model the disorder but
6
63.18 (50) [M þ H] , 544.08 (100) [M ꢀ PEt
3
2
since the other three independent molecules in H c are well
behaved we have included this data.
[
Cp*Ir(BiphenS
This was prepared as per complex 3a using [Cp*IrCl
150 mg, 0.29 mmol) and [Biphen(SH) ] (101 mg, 0.46 mmol) with
2 3
)PEt ] (4c)
2 3
PEt ]
Tables 7e9 list the details of data collections and refinements.
(
2
refluxing for 5 h 4c was obtained as a yellow/orange solid (154 mg,
Appendix A. Supplementary material
Table 9
Crystallographic data for H
CCDC 1018981e1018992 contain the supplementary crystallo-
graphic data for this paper. These data can be obtained free of
charge from The Cambridge Crystallographic Data Center via www.
ccdc.cam.ac.uk/data_request/cif.
2
a, H
2
b, H
2
c and H
2
d.
H
2
a
H
2
b
H
2
c
2
H d
Empirical formula
M
C
10
H
8
S
2
C
12
H
10
S
2
C
12
H
10
S
2
6 6 2
C H S
142.23
192.29
218.33
218.33
Crystal system
Space group
a [Å]
Monoclinic
P2(1)/c
6.3606(17)
14.849(4)
18.532(6)
90
90.307(8)
90
1750.3(9)
8
Monoclinic
P2(1)/c
11.751(5)
11.229(3)
15.804(6)
90
110.912(12)
90
1947.9(13)
8
Triclinic
Pꢀ1
Triclinic
Pꢀ1
References
7.6315(5)
11.6376(10)
24.6857(18)
100.640(4)
96.102(5)
93.939(5)
2133.7(3)
8
7.6271(6)
10.1076(8)
10.1458(14)
95.625(13)
111.148(9)
108.956(10)
669.07(15)
4
[
[
[
1] A.M. Bond, R.L. Martin, Coord. Chem. Rev. 54 (1984) 23e98.
2] R.P. Burns, C.A. McAuliffe, Adv. Inorg. Chem. Radiochem. 22 (1979) 303e348.
3] R.P. Burns, F.P. McCullough, C.A. McAuliffe, Adv. Inorg. Chem. Radiochem. 23
b [Å]
c [Å]
ꢁ
a
b
g
[ ]
(1980) 211e280.
ꢁ
[ ]
[4] R. Eisenberg, in: Prog. Inorg. Chem., John Wiley & Sons, Inc., 2007, pp.
ꢁ
[ ]
295e369.
3
V [Å ]
[5] J.R. Phillips, J.C. Poat, A.M.Z. Slawin, D.J. Williams, P.T. Wood, J.D. Woollins,
J. Chem. Soc. Dalton Trans. (1995) 2369e2375.
[6] J.D. Woollins, in: S.C. Mitchell (Ed.), Biological Interactions of Sulfur Com-
pounds, Taylor & Francis, London, 1996, pp. 1e19.
Z
r
calcd. [g cmꢀ3]
1.459
0.541
1.489
4.960
1.359
0.453
1.412
6.793
ꢀ
m
[cm 1
]
[
[
[
7] B.K. Teo, F. Wudl, J.H. Marshall, A. Kruger, J. Am. Chem. Soc. 99 (1977)
349e2350.
8] B.K. Teo, F. Wudl, J.J. Hauser, A. Kruger, J. Am. Chem. Soc. 99 (1977)
862e4863.
9] B.K. Teo, P.A. Snyder-Robinson, Inorg. Chem. 17 (1978) 3489e3497.
Measured refln.
Unique refln.
12,608
3197
0.0574
0.1521
12,542
3545
0.0398
0.1349
29,581
7716
0.1542
0.4835
10,325
2434
0.0516
0.1406
2
R [I > 2
s(I)]
4
wR

16
P.S. Nejman et al. / Journal of Organometallic Chemistry 776 (2015) 7e16
[
[
10] B.K. Teo, P.A. Snyder-Robinson, Inorg. Chem. 18 (1979) 1490e1495.
11] B.K. Teo, P.A. Snyder-Robinson, J. Chem. Soc. Chem. Commun. (1979)
55e256.
[31] S. Cossu, G. Delogu, D. Fabbri, P. Maglioli, Org. Prep. Proced. Int. 23 (1991)
455e457.
2
[32] K. Yui, Y. Aso, T. Otsubo, F. Ogura, Bull. Chem. Soc. Jpn. 61 (1988) 953e959.
[33] J. Zhao, Z. Wei, X. Zeng, X. Liu, Dalton Trans. 41 (2012) 11125e11133.
[34] E. Block, V. Eswarakrishnan, M. Gernon, G. Ofori-Okai, C. Saha, K. Tang,
J. Zubieta, J. Am. Chem. Soc. 111 (1989) 658e665.
[12] B.K. Teo, P.A. Snyder-Robinson, Inorg. Chem. 20 (1981) 4235e4239.
[13] B.K. Teo, V. Bakirtzis, P.A. Snyder-Robinson, J. Am. Chem. Soc. 105 (1983)
6330e6332.
[
[
14] B.K. Teo, P.A. Snyder-Robinson, Inorg. Chem. 23 (1984) 32e39.
15] W.P. Bosman, H.G.M. van der Linden, J. Chem. Soc. Chem. Commun. (1977)
[35] I. Ara, J.R. Berenguer, E. Eguiz aꢀ bal, J. Forni eꢀ s, E. Lalinde, A. Martín, F. Martínez,
Organometallics 17 (1998) 4578e4596.
7
14e715.
[36] J.W. Kang, K. Moseley, P.M. Maitlis, J. Am. Chem. Soc. 91 (1969) 5970e5977.
[37] R. Xi, M. Abe, T. Suzuki, T. Nishioka, K. Isobe, J. Organomet. Chem. 549 (1997)
117e125.
[
[
16] R.J. Wright, C. Lim, T.D. Tilley, Chem. Eur. J. 15 (2009) 8518e8525.
17] A.P.S. Samuel, D.T. Co, C.L. Stern, M.R. Wasielewski, J. Am. Chem. Soc. 132
(
2010) 8813e8815.
[38] S.M. Aucott, H.L. Milton, S.D. Robertson, A.M.Z. Slawin, J.D. Woollins, Heteroat.
Chem. 15 (2004) 530e542.
[
[
[
[
18] P. Li, S. Amirjalayer, F. Hartl, M. Lutz, B.d. Bruin, R. Becker, S. Woutersen,
J.N.H. Reek, Inorg. Chem. 53 (2014) 5373e5383.
19] J. Ballmann, S. Dechert, S. Demeshko, F. Meyer, Eur. J. Inorg. Chem. (2009)
[39] S.M. Aucott, H.L. Milton, S.D. Robertson, A.M.Z. Slawin, J.D. Woollins, Heteroat.
Chem. 16 (2005) 346e351.
[40] M.L. Clarke, D.J. Cole-Hamilton, D.F. Foster, A.M.Z. Slawin, J.D. Woollins,
J. Chem. Soc. Dalton Trans. (2002) 1618e1624.
3219e3225.
20] K. Charreteur, M. Kdider, J.-F. Capon, F. Gloaguen, Y.F. Petillon,
P. Schollhammer, J. Talarmin, Inorg. Chem. 49 (2010) 2496e2501.
21] A. Albers, S. Demeshko, S. Dechert, C.T. Saouma, J.M. Mayer, F. Meyer, J. Am.
Chem. Soc. 136 (2014) 3946e3954.
[41] B.A. Paz-Michel, F.J. Gonzalez-Bravo, L.S. Hernandez-Muneoz, M.A. Paz-San-
doval, Organometallics 29 (2010) 3709e3721.
[42] B. Paz-Michel, M. Cervantes-Vazquez, M.A. Paz-Sandoval, Inorg. Chim. Acta
361 (2008) 3094e3102.
[
[
[
22] C. Topf, U. Monkowius, G. Kn o€ r, Inorg. Chem. Commun. 21 (2012) 147e150.
23] R. Conry, A.A. Tipton, J. Biol. Inorg. Chem. 6 (2001) 359e366.
[43] X.-Q. Xiao, G.-X. Jin, J. Organomet. Chem. 693 (2008) 316e320.
[44] G.-L. Wang, Y.-J. Lin, O. Blacque, H. Berke, G.-X. Jin, Inorg. Chem. 47 (2008)
2940e2942.
24] R.L. McNaughton, A.A. Tipton, N.D. Rubie, R.R. Conry, M.L. Kirk, Inorg. Chem.
39 (2000) 5697e5706.
[
25] M.R. Malachowski, M. Adams, N. Elia, A.L. Rheingold, R.S. Kelly, J. Chem. Soc.
[45] Z.-J. Yao, B. Xu, X.-K. Huo, G.-X. Jin, J. Organomet. Chem. 747 (2013) 85e89.
[46] S. Kuwata, T. Nagano, A. Matsubayashi, Y. Ishii, M. Hidai, Inorg. Chem. 41
(2002) 4324e4330.
[47] S.M. Aucott, H.L. Milton, S.D. Robertson, A.M. Slawin, J.D. Woollins, Dalton
Trans. (2004) 3347e3352.
Dalton Trans. (1999) 2177e2182.
[26] E. Erkizia, R.R. Conry, Inorg. Chem. 39 (2000) 1674e1679.
27] P.R. Stafford, T.B. Rauchfuss, A.K. Verma, S.R. Wilson, J. Organomet. Chem. 526
[
(
1996) 203e214.
[
28] S.M. Aucott, P. Kilian, H.L. Milton, S.D. Robertson, A.M.Z. Slawin, J.D. Woollins,
[48] W.L.F. Armarego, C.L.L. Chai, Purification of Laboratory Chemicals, sixth ed.,
Butterworth-Heinemann, Oxford, 2009.
Inorg. Chem. 44 (2005) 2710e2718.
[
[
29] A.J. Ashe, J.W. Kampf, P.M. Savla, Heteroat. Chem. 5 (1994) 113e119.
30] C.G.M. Benson, C.M. Schofield, R.A.M. Randall, L. Wakefield, F.R. Knight,
A.M.Z. Slawin, J.D. Woollins, Eur. J. Inorg. Chem. (2013) 427e437.
[49] G. Sheldrick, Acta Crystallogr. A 64 (2008) 112e122.
́
́
́