Reactions of Bis(chalcogenolato) Complexes [(-5-C 5Me5)Ir(CO)(ETol)2] (E = Se, S; Tol = p -Tolyl) with [Pt(PPh3)3]. Formation of tri- or dinuclear mixed-metal complexes with bridging chalco

Article abstract of DOI:10.1021/om9010609

Treatment of [Cp*Ir(CO)(SeTol)₂] (Cp* = - ⁵-C₅Me₅, Tol = p-tolyl) with 2 equiv of [Pt(PPh₃)₃] in toluene at reflux resulted in the insertion of Pt(PPh₃) groups into Se-Tol bonds

Full text of DOI:10.1021/om9010609

2254 Organometallics 2010, 29, 2254–2259
DOI: 10.1021/om9010609
Reactions of Bis(chalcogenolato) Complexes [(η5-C5Me5)Ir(CO)(ETol)2]
(E = Se, S; Tol = p-Tolyl) with [Pt(PPh3)3]. Formation of Tri- or
Dinuclear Mixed-Metal Complexes with Bridging Chalcogenido or
Chalcogenolato Ligands
Takafumi Nakagawa, Hidetake Seino, and Yasushi Mizobe*
Institute of Industrial Science, The University of Tokyo, Komaba, Meguro-ku, Tokyo 153-8505, Japan
Received December 10, 2009
Treatment of [Cp*Ir(CO)(SeTol)2] (Cp*=η5-C5Me5, Tol=p-tolyl) with 2 equiv of [Pt(PPh3)3] in
toluene at reflux resulted in the insertion of Pt(PPh3) groups into Se-Tol bonds to give the triangular
cluster with capped Se ligands [Cp*Ir(μ3-Se)2{PtTol(PPh3)}2] (5). By stirring under CO atmosphere,
5 in solution was readily converted to [Cp*Ir(CO)(μ3-Se)2{PtTol(PPh3)}2] (2b), which returned to 5 in
toluene at reflux. On the other hand, reaction of [Cp*Ir(CO)(STol)2] with an equimolar amount of
[Pt(PPh3)3] afforded the thiolato-bridged dinuclear complex [Cp*Ir(CO)(μ-STol)Pt(STol)(PPh3)] (6)
through the insertion of the Pt center into the Ir-S bond, and that with 2 equiv of [Pt(PPh3)3] in
toluene at reflux led to the incorporation of the second Pt fragment to the core of 6 to give the
thiolato-bridged triangular cluster [Cp*Ir{Pt(PPh3)}2(μ2-CO)(μ2-STol)2] (7). An X-ray diffraction
study has been carried out to determine the detailed structures of 2b, 5, 6, and [Cp*Ir{Pt(PPh3)}2-
(μ2-CO)(μ2-SPh)2], which is the SPh analogue of 7.
Introduction
complex 1a with [Pt(PPh3)3] to those of bis(selenolato) and
bis(thiolato) analogues [Cp*Ir(CO)(ETol)2] (E = Se (1b),
S (1c)). As expected, it has been revealed that the reaction
courses are sharply affected by the nature of the chalcogen
atoms. In this paper we describe the results of these reactions
and the structures of new tri- and dinuclear Ir-Pt complexes
having bridging selenium and sulfur ligands obtained here.
Multimetallic complexes with sulfur and heavier chalcogen
ligands are continuously attracting much attention because
of their relevance to the active sites of certain biological and
industrial catalysts.2,3
In a previous paper,1 we have reported that organic ditellu-
ride TolTeTeTol (Tol = p-tolyl) reacts smoothly with [Cp*Ir-
(CO)2] (Cp* = η5-C5Me5) to give bis(tellurolato) complex
[Cp*Ir(CO)(TeTol)2] (1a), and then 1a is treated with 2 equiv
of [Pt(PPh3)3] or [Pd(PPh3)4] at room temperature to afford
bis(μ-tellurido) clusters [Cp*Ir(CO)(μ3-Te)2{MTol(PPh3)}2]
(M = Pt (2a), Pd (3a)) via the insertion of the Pt(PPh3) or
Pd(PPh3) groups into the Te-Tol bonds (Scheme 1). From
the reaction of 1a with an equimolar amount of [Pt(PPh3)3],
the dinuclear complex containing both μ-tellurido and μ-tell-
urolato ligands [Cp*Ir(CO)(μ-Te)(μ-TeTol)PtTol(PPh3)] (4)
was isolated as the intermediate stage toward 2a. These
findings have demonstrated that the easily available, organic
ditelluride TolTeTeTol can be used as the convenient tell-
urium source soluble in organic media to derivatize the tell-
urido complexes. It has also been emphasized that the chemis-
try of the heavier chalcogen complexes,2 especially tellurium
complexes, is still poorly advanced in contrast to that of the
complexes with sulfur ligands.
Results and Discussion
Reaction of 1b with [Pt(PPh3)3]. The reaction of 1b with
[Pt(PPh3)3] did take place in THF and toluene even at room
temperature. However, the NMR spectra showed the for-
mation of complicated mixtures, and no characterizable pro-
ducts were isolated therefrom. On the other hand, under more
drastic conditions the reaction system becomes simple. Thus,
when the mixture of 1b and 2 equiv of [Pt(PPh3)3] in toluene
was heated to reflux for 3 h, the trinuclear bis(selenido) clus-
ter [Cp*Ir(μ3-Se)2{PtTol(PPh3)}2] (5) was isolated from the
reaction mixture in 33% yield as green crystals (Scheme 2).
To clarify the difference in reactivities between the com-
plexes with the tellurium and the lighter chalcogen ligands, we
have extended the study on the reactions of the bis(tellurolato)
(3) (a) Rao, P. V.; Holm, R. H. Chem. Rev. 2004, 104, 527. (b) Lee,
S. C.; Holm, R. H. Chem. Rev. 2004, 104, 1135. (c) Llusar, R.; Uriel, S. Eur.
J. Inorg. Chem. 2003, 1271. (d) Degroot, M. W.; Corrigan, J. F. In
Comprehensive Coordination Chemistry II; McCleverty, J. A.; Meyer,
T. J., Eds.; Elsevier: New York, 2004; Vol. 7, pp 57-123. (e) Brorson, M.;
King, J. D.; Kiriakidou, K.; Prestopino, F.; Nordlander, E. In Metal Clusters
in Chemistry; Braunstein, P.; Oro, L. A.; Raithby, P. R., Eds.; Wiley-VCH:
Weinheim, Germany, 1999; pp 725-741. (f) Blower, P. J.; Dilworth, J. R.
Coord. Chem. Rev. 1987, 76, 121.
*Corresponding author. E-mail: ymizobe@iis.u-tokyo.ac.jp.
(1) Nakagawa, T.; Seino, H.; Nagao, S.; Mizobe, Y. Angew. Chem.,
Int. Ed. 2006, 45, 7758.
(2) (a) Gimeno, M. C. In Handbook of Chalcogen Chemistry; Derillanova,
F. A., Ed.; RSC Publishing: Cambridge, UK, 2009; pp 33-80. (b) Singh, A. J.;
Sharma, S. Coord. Chem. Rev. 2000, 209, 49. (c) Parkin, G. Prog. Inorg. Chem.
1998,47, 1. (d) Trnka, T. M.; Parkin, G. Polyhedron 1997, 16, 1031. (e) Arnold, J.
Prog. Inorg. Chem. 1995, 43, 353.
r
pubs.acs.org/Organometallics
Published on Web 04/23/2010
2010 American Chemical Society

Article
Organometallics, Vol. 29, No. 10, 2010 2255
Scheme 1
Scheme 2
Figure 1. ORTEP drawing of 2b (50% probability level). One of
the two crystallographically independent molecules is depicted.
For clarity, all hydrogen atoms are omitted and only the ipso-C
atoms of the Ph groups are shown for PPh3 ligands.
Insertion of Pt into Se-Tol bonds resulted in the formation
of the IrPt2(μ3-Se)2 core analogous to 2a, but the CO ligand
was lost from the Ir site. As for the reaction of 1b with 1 equiv
of [Pt(PPh3)3], no tractable products were obtained even
after refluxing in toluene.
For the formation of 5, dissociation of CO is presumed to
take place owing to the drastic conditions employed. Thus,
when the reaction mixture containing crude 5 in toluene was
stirred under CO (1 atm) at room temperature, the color of
the solution changed rapidly from green to orange. From the
resultant solution, [Cp*Ir(CO)(μ3-Se)2{PtTol(PPh3)}2] (2b)
was isolated in 38% yield based on 1b as red crystals. It has
been confirmed independently by recording the NMR spec-
tra of the reaction mixtures that 5 is quantitatively converted
into 2b by stirring its THF solution under CO (1 atm) at
room temperature, while 2b, when dissolved in toluene under
N2 and heated at reflux, is transformed back to 5 exclusively
(Scheme 2). It is to be noted that in the case of the tellurido
cluster 2a the Ir-CO bond is intact even after heating in
toluene at reflux.
Figure 2. ORTEP drawing of 5 (50% probability level). For
clarity, all hydrogen atoms are omitted and only the ipso-C
atoms of the Ph groups are shown for PPh3 ligands.
˚
Table 1. Selected Interatomic Distances (A) and Angles (deg) in
2b and 5
2b (molecule 1)
2b (molecule 2)
5
Structures of 2b and 5. Single-crystal X-ray analysis has
disclosed the detailed structures for 2b and 5, whose ORTEP
drawings are shown in Figures 1 and 2, respectively. Selected
interatomic distances and angles are listed in Table 1. Crystals
of 2b contained two crystallographically independent mole-
cules, whose structrures are essentially the same.
Cluster 2b, consisting of a 50-electron IrPt2 core, is isostruc-
tural with 2a. Thus, the Ir(III) center, with three-legged piano-
stool geometry, is connected with two square-planar Pt(II)
centers by two μ3-Se ligands. Two PPh3 ligands have an anti
(a) Interatomic Distances
Ir Pt(1)
3 3 3
3.6062(8)
3.5308(7)
3.1068(9)
2.528(2)
2.508(1)
2.537(2)
2.481(2)
2.478(1)
2.557(2)
3.6211(8)
3.0931(7)
3.1961(6)
3.2691(6)
2.422(1)
2.416(1)
2.466(1)
2.498(1)
2.517(1)
2.449(1)
Ir Pt(2)
3 3 3
3.5514(7)
3.0201(8)
2.521(1)
2.510(2)
2.493(2)
2.517(2)
2.541(1)
2.490(2)
Pt(1) Pt(2)
3 3 3
Ir-Se(1)
Ir-Se(2)
Pt(1)-Se(1)
Pt(1)-Se(2)
Pt(2)-Se(1)
Pt(2)-Se(2)
disposition with respect to the Pt Pt vector, and there are
no bonding interactions between metals. However, inter-
3 3 3
(b) Interatomic Angles
Se(1)-Ir-Se(2)
Se(1)-Ir-C(11)
Se(2)-Ir-C(11)
Se(1)-Pt(1)-Se(2)
Se(1)-Pt(2)-Se(2)
75.87(4)
92.6(4)
92.7(4)
76.05(5)
85.04(4)
atomic distances in the core of 2b (Ir Pt: 3.5308(7)-
3 3 3
93.1(5)
91.0(5)
76.42(5)
76.04(4)
˚
3.6211(8) A; Pt Pt: 3.0201(8) and 3.1068(9) A) are all much
˚
3 3 3
˚
shorter than those in 2a (Ir Pt: 3.8054(5)-3.8588(5) A;
76.18(5)
75.87(4)
82.41(4)
82.36(4)
3 3 3
˚
Pt Pt: 3.1543(4) and 3.2523(7) A), and hence the former is
3 3 3

2256 Organometallics, Vol. 29, No. 10, 2010
Nakagawa et al.
˚
Figure 3. Comparison of selected interatomic distances (A) related to the steric crowding in 2a, 2b, and 5 (from left to right). Values of
two crystallographically independent molecules are given for 2a and 2b.
apparently sterically more congested than the latter. This may
result in the more severe steric repulsion between Cp* and the
PtTol(PPh3) fragment as well as that between CO and the
PtTol(PPh3) scaffold, as shown in Figure 3, which presum-
ably accounts for the finding that the CO in 2b is more
dissociative. The ν(CO) values at 1983 and 1979 cm-1 in 2b
and 2a, respectively, differ only slightly, suggesting that the
electronic factor is essentially negligible with respect to the
difference in the dissociating ability of CO ligands between
these two.
The 48-electron cluster 5 consists of the Ir(III) center with
a two-legged geometry together with two square-planar Pt(II)
˚
centers. The Ir Pt distances at 3.0931(7) and 3.1961(6) A
3 3 3
are significantly shorter than those in 2b, but nevertheless,
owing to the change in the geometry around Ir caused by the
loss of CO, steric repulsion apparently diminishes to a great
extent, as depicted in Figure 3.
The 1H and 31P{1H} NMR spectra have disclosed that 2b
Figure 4. ORTEP drawing of 6 (50% probability level). Hydro-
gen atoms are omitted for clarity.
exists as a mixture of two isomers in a ratio of 9:1 in C6D6
solution at room temperature. This feature can be interpre-
ted in terms of the equilibrium between the X-ray analyzed
anti isomer and the syn isomer (eq 1), which was also obser-
ved for 2a but in a ratio of 4:1. We propose that the latter
isomer is less stable due to the larger repulsion between two
PPh3 ligands. Similar isomerization also occurs for 5 in soltion,
where the anti:syn ratio is ca. 10 in C6D6.
THF at room temperature to give the dinuclear complex [Cp*Ir-
(CO)(μ-STol)Pt(STol)(PPh3)] (6) in moderate yield (eq 2).
Complex 6 is thermally stable, and its structure is retained even
after heating in toluene at reflux. In this reaction, insertion of
Pt occurs at one Ir-S bond in 1c to afford an Ir-Pt-STol
array and the Ir-Pt bond is bridged by the other STol ligand.
Complex 6 has been characterized by X-ray diffraction
(Figure 4, Table 2).
The related triangular Ir(III)2Pt(II) core with two capped
Se ligands [(Cp*Ir)2(PtCl2)(μ3-Se)2] was reported previously,4
while the Pt(II)3(μ3-Se)2 cores were fully characterized for
[Pt(PPh3)2(μ3-Se)2{Pt(cod)}2][PF6]2 and [Pt(cod)(μ3-Se)2-
{Pt(PPh3)2}2][PF6]2.5
Complex 6 has a formal Ir(II)Pt(I) core with an Ir-Pt
bond of 2.6918(3) A. If this bonding interaction is ignored,
˚
the Ir and Pt centers have two-legged piano-stool and seve-
rely distorted T-shaped structures, respectively. Around Pt,
˚
Reactions of 1c with [Pt(PPh3)3]. Reaction of the bis(thiolato)
complex 1c with 1 equiv of [Pt(PPh3)3] proceeded cleanly in
the Pt-μ-S(1) distance at 2.270(1) A is significantly shorter
˚
than the terminal thiolato Pt-S(2) bond length (2.327(1) A).
Complex 6 shows a characteristic ν(CO) band at 1951 cm-1
,
which is much lower than 1991 cm-1 observed for the parent
1c. This might be interpreted by the difference in the formal
oxidation state of Ir centers, viz., þ2 in 6 and þ3 in 1c. The
(4) Nagao, S.; Seino, H.; Hidai, M.; Mizobe, Y. J. Organomet. Chem.
2003, 669, 124.
(5) Teo, J. S. L.; Vittal, J. J.; Henderson, W.; Hor, T. S. A. Inorg.
Chem. 2002, 41, 1194.

Article
Organometallics, Vol. 29, No. 10, 2010 2257
0
˚
Table 2. Selected Bond Distances (A) and Angles (deg) in 6 and 7
When 1c was reacted with 2 equiv of [Pt(PPh3)3] in toluene
at room temperature, the reaction mixture contained only 6
and Pt-PPh3 complexes. In contrast, when this mixture was
heated to reflux for 5 h, [Cp*Ir{Pt(PPh3)}2(μ2-CO)(μ2-STol)2]
(7) was obtained (eq 3), where the second {Pt(PPh3)} frag-
ment is incorporated with concurrent binding to the C atom
of the CO ligand as well as the S atom of the terminal STol
ligand in 6, affording the triangular IrPt2 core with one
μ2-CO and two μ2-STol ligands. Unfortunately, 7 was not
isolable as an analytically pure form and was characterized
only spectroscopically. On the other hand, analogous treat-
ment of the SPh congener [Cp*Ir(CO)(SPh)2] (1c0) with
2 equiv of [Pt(PPh3)3] led to the isolation of single crystals
of [Cp*Ir{Pt(PPh3)}2(μ2-CO)(μ2-SPh)2] (70) (eq 3), whose
structure could be determined in a well-defined manner. The
ORTEP drawing is shown in Figure 5, and selected metrical
parameters are listed in Table 2.
6
(a) Interatomic Distances
Ir-Pt
Pt-S(1)
2.6918(3)
2.270(1)
Ir-S(1)
Pt-S(2)
2.318(1)
2.327(1)
(b) Interatomic Angles
S(1)-Ir-C(11)
S(1)-Pt-P(1)
94.1(2)
110.84(5)
S(1)-Pt-S(2)
S(2)-Pt-P(1)
159.01(5)
89.43(5)
7’a
(a) Interatomic Distances
Ir-Pt(1)
Pt(1)-Pt(2)
Ir-C(11)
Pt(1)-S(1)
Pt(2)-S(2)
2.7043(5)
2.8061(4)
2.09(1)
2.307(3)
2.418(2)
Ir-Pt(2)
2.6718(5)
Ir-S(1)
Pt(1)-S(2)
Pt(2)-C(11)
2.252(2)
2.349(2)
1.94(1)
(b) Interatomic Angles
Pt(1)-Ir-Pt(2)
Ir-Pt(2)-Pt(1)
S(1)-Pt(1)-S(2)
S(2)-Pt(1)-P(1)
S(2)-Pt(2)-C(11)
62.92(1)
59.10(1)
144.43(7)
106.76(6)
143.2(3)
Ir-Pt(1)-Pt(2)
57.97(1)
98.5(2)
108.81(8)
111.54(7)
105.2(3)
S(1)-Ir-C(11)
S(1)-Pt(1)-P(1)
S(2)-Pt(2)-P(2)
P(2)-Pt(2)-C(11)
a Data for one of the two disordered molecules with larger occupancy.
Cluster 70 has a triangular IrPt2 core with a 46-electron
˚
count, where the Ir-Pt distances at 2.7043(5) and 2.6718(5) A
˚
as well as the Pt-Pt separation of 2.8061(4) A indicate the
presence of metal-metal single bonds. One Ir-Pt bond is
bridged by the CO ligand, while the other two edges are co-
ordinated with μ2-SPh groups. Two P atoms of PPh3 ligands
are almost coplanar with the IrPt2 triangle, whereas the Cp*
ligand and S(2) atom are directed to one side of the IrPt2
plane and the S(1) and C(11) atoms are situated at the
opposite side of this plane. The ν(CO) band observed at
1731 cm-1 in the IR spectrum is consistent with its μ2 bridg-
ing mode. The triangular Pt3 core with μ2-thiolato bridges
was crystallographically characterized for, for example, the
Pt(II) cluster without Pt-Pt bonds, [Pt3{μ2-S-o-C6H4-
NdCH-(π-C5H3)Fe(π-C5H5)}3-κ3-S,N,C],10 while that with
μ2-CO ligands was presumed for, for example, Pt(0) clusters
without Pt-Pt bonds, [{Pt(PR3)}3(μ2-CO)3].11
Figure 5. ORTEP drawing of 70 (50% probability level). Hydro-
gen atoms are omitted for clarity.
Conclusions
dinuclear Ir(II) complex [{Cp*Ir(CO)}2(μ-S)] has been repor-
ted to exhibit a ν(CO) band at 1929 cm-1 6
.
The reaction of the selenolato complex 1b with [Pt(PPh3)3]
proceeded similarly to that previously reported for the tell-
urolato complex 1a, yielding the IrPt2(μ3-Se)2 core via the
insertion of Pt into the Se-Tol bonds. However, more dras-
tic conditions were required for 1b. In contrast, the thiolato
analogue 1c is amenable to the insertion of Pt into the Ir-S
bond to give first the Ir(μ-STol)Pt-STol complex and then
the triangular IrPt2(μ2-STol)2 cluster. These findings are
consistent with the findings previously reported for the
reactions of Ph2E (E = Te, Se, S) with [Pt(PEt3)3], where
the oxidative addition of Ph-E bonds proceeds most readily
Dinuclear cores supported by only one κ1 S atom ligand
are still rare, which include, for example, [Pd(C6F5)(phen)-
(μ-SC6F5)Pt(C6F5)(dppe)], in which the Pd and Pt centers
without a direct bonding interaction are connected by a
SC6F5 ligand.7 The Ir and Mo centers without an Ir-Mo
bond in [{Cp*IrH(PPh3)}(μ-S){MoCp*Cl(NO)}] are com-
bined by a sulfido ligand,8 while the Ir-Ir single bonds in
[{Cp*Ir(CO)}2(μ-S)] and [{Cp*Ir(PMe3)}(μ-S){Ir(PPh3)-
(NO)}] are supported by a bridging S ligand.6,9
(6) Jones, W. D.; Chin, R. M. J. Am. Chem. Soc. 1994, 116, 198.
ꢀ
ꢀ
(7) Uson, R.; Uson, M. A.; Herrero, S.; Rello, L. Inorg. Chem. 1998,
37, 4473.
(8) Arashiba, K.; Matsukawa, S.; Tanabe, Y.; Kuwata, S.; Ishii, Y.
(10) Nagasawa, I.; Kawamoto, T.; Kuma, H.; Kushi, Y. Chem. Lett.
1996, 921.
Inorg. Chem. Commun. 2008, 11, 587.
(9) Hattori, T.; Matsukawa, S.; Kuwata, S.; Ishii, Y.; Hidai, M.
Chem. Commun. 2003, 510.
(11) (a) Browning, C. S.; Farrar, D. H.; Gukathasan, R. R.; Morris,
S. A. Organometallics 1985, 4, 1750. (b) Ros, R.; Facchin, G.; Tassan, A.;
Roulet, R.; Laurenczy, G.; Lukacs, F. J. Cluster Sci. 2001, 12, 99.

2258 Organometallics, Vol. 29, No. 10, 2010
Nakagawa et al.
for E=Te and becomes more difficult for E=Se and S in this
order.12 It has also been demonstrated that the reactions of
the cluster [Os3(CO)10(MeCN)2] with furan and its heavier
chalcogen analogues C4H4E (E = O, S, Se, Te) lead to the
compounds formed by C-H bond cleavage for E=O and S
or by C-E cleavage for E=Se and Te.13 These data and our
result clearly present that the reactivity of chalcogen-carbon
bonds toward transition metal complexes increases stepwise
in the order S, Se, and Te.
2b-anti: 1H NMR (C6D6): δ 1.61 (s, 15H, Cp*), 2.12, 2.20 (s, 3H
each, Me), 6.70, 6.82, 7.47, 7.58 (d, J=8.0 Hz, 2H each, C6H4).
31P{1H} NMR (C6D6): δ 11.1 (d with 195Pt and 77Se satellites,
J
P-P =5 Hz, JPt-P =3920 and 8 Hz, JSe-P =85 and ∼20 Hz),
12.8 (d with 195Pt and 77Se satellites, JP-P =5 Hz, JPt-P =3830
and 8 Hz, JSe-P=76 and ∼20 Hz). For 2b-syn: 1H NMR (C6D6):
δ 1.63 (s, 15H, Cp*); the signals due to Tol are overlapping with
those of 2b-anti). 31P{1H} NMR (C6D6): δ 9.5 (d, JP-P=7 Hz),
10.2 (d, JP-P=7 Hz); the 195Pt and 77Se satellites were too weak
to be assigned. The ratio of 2b-anti:2b-syn was ca. 9.
It should be mentioned finally that the reactions of 1b and
1c with [Pd(PPh3)4] were also carried out. The spectroscopic
evidence supported that [Cp*Ir(μ3-Se)2{PdTol(PPh3)}2] and
[Cp*Ir{Pd(PPh3)}2(μ2-CO)(μ2-STol)2] were produced simi-
larly. However, none of these could be isolated either in
analytically pure form or as single crystals for X-ray diffrac-
tion (see Supporting Information).
Preparation of 6. Into a THF solution (5 mL) of 1c (295 mg,
0.490 mmol) was added [Pt(PPh3)3] (485 mg, 0.494 mmol), and
the mixture was stirred at room temperature for 2 days. Addi-
tion of hexane to the concentrated product solution gave 6 as red
crystals (305 mg, 58% yield). Anal. Calcd for C43H44OPS2IrPt:
C, 48.76; H, 4.19. Found: C, 49.20; H, 4.00. IR (KBr): ν(CO),
1951 cm-1. 1H NMR (C6D6): δ 1.81 (d, J=1.6 Hz, 15H, Cp*),
1.87, 2.13 (s, 3H each, Me), 6.60, 6.90, 7.58, 7.93 (d, J=8.0 Hz,
2H each, C6H4). 31P{1H} NMR (C6D6): δ 15.3 (s with 195Pt
satellites, JPt-P =3735 Hz).
Experimental Section
Preparation of 7. A mixture of 1c (59 mg, 0.10 mmol) and
[Pt(PPh3)3] (200 mg, 0.204 mmol) in toluene (5 mL) was stirred
at room temperature. The NMR spectra of the reaction mixture
indicated the presence of only 6 and Pt-PPh3 complexes. Then
the mixture was heated to reflux for 5 h, and after cooling to
room temperature the resultant dark green solution was evapo-
rated to dryness in vacuo. The spectral data of the residue are
diagnostic of the formation of 7, but analytically pure crystals
were not available in spite of the repeated purification. IR
General Procedures. All manipulations were carried out under
N2 using standard Schlenk techniques. Solvents were dried by
common methods and distilled under N2 before use. Complex
[Cp*Ir(CO)(SPh)2] was prepared according to the literature
method,14 and related 1b and 1c were synthesized by essentially
the same but slightly modified procedure. Complex [Pt(PPh3)3]
was obtained as described previously.15
IR and NMR spectra were obtained by a JASCO FT-IR 420
or a JEOL alpha-400 spectrometer, respectively. For the 1H
NMR data, the signals due to PPh3 are omitted. The 31P{1H}
NMR spectra containing both 195Pt and 77Se satellites were ana-
lyzed by line-shape simulation using gNMR software.16 Where
two JPt-P values are given for one 31P signal, the smaller one cor-
responds to the long-range coupling constant. Elemental analyses
were done with a Perkin-Elmer 2400 series II CHN analyzer.
Preparation of 5. A mixture of 1b (71 mg, 0.10 mmol) and [Pt-
(PPh3)3] (204 mg, 0.207 mmol) in toluene (10 mL) was refluxed
for 3 h. After cooling to room temperature, the resultant dark
green solution was concentrated, and then hexane was added to
precipitate 5 as green crystals (55 mg, 33% yield). Anal. Calcd
for C60H59P2Se2IrPt2: C, 45.54; H, 3.76. Found: C, 45.39; H,
3.61. For 5-anti: 1H NMR (C6D6): δ 1.54 (s, 15H, Cp*), 2.19 (s,
6H, Me), 6.70, 7.31 (d, J = 8.0 Hz, 4H each, C6H4). 31P{1H}
(KBr): ν(CO), 1731 cm-1. 1H NMR (C6D6): δ 2.07 (d, JH-P
=
0.8 Hz, 15H, Cp*), 1.82, 1.97 (s, 3H each, Me), 6.07, 6.69, 7.58,
7.93 (d, J=8.0 Hz, 2H each, C6H4). 31P{1H} NMR (C6D6): δ 8.7
(d with 195Pt satellites, JP-P=32 Hz, JPt-P=4510 and 315 Hz),
40.4 (d with 195Pt satellites, JP-P = 32 Hz, JPt-P = 6030 and
160 Hz).
Preparation of 70. A mixture containing [Cp*Ir(CO)(SPh)2]
(59 mg, 0.10 mol) and [Pt(PPh3)3] (200 mg, 0.204 mmol) in
toluene (5 mL) was refluxed for 5 h. After cooling to room tem-
perature, the resulting dark green solution was dried in vacuo.
The residue was washed with MeOH and then crystallized from
benzene-hexane. The yield of 70 as green crystals was 16 mg
(11%). Anal. Calcd for C59H55OP2S2IrPt2: C, 47.61; H, 3.72.
Found: C, 47.64; H, 3.83. IR (KBr): ν(CO), 1731 cm-1 1H
.
NMR (C6D6): δ 2.06 (d, JH-P =0.8 Hz, 15H, Cp*), 6.30 (t, J=
6.0 Hz, 2H, SPh), 6.44 (t, J = 6.0 Hz, 1H, SPh), 6.84 (m, 4H,
SPh), 7.43 (m, 3H, SPh). 31P{1H} NMR (C6D6): δ 8.6 (d with
195Pt satellites, JP-P = 32 Hz, JPt-P = 4480 and 320 Hz), 40.5
(d with 195Pt satellites, JP-P=32 Hz, JPt-P=6020 and 120 Hz).
NMR (C6D6): δ 17.0 (m with 195Pt and 77Se satellites, 1JPt-P
=
4230 Hz, 2JSe(trans)-P =68 Hz); other coupling constants (<6 Hz)
could not be assigned unambiguously because of a highly com-
plicated PP0PtPt0SeSe0 spin system. For 5-syn: 1H NMR (C6D6):
δ 1.57 (s, 15H, Cp*), 2.16 (s, 6H, Me), 6.70, 7.31 (C6H4, over-
lapping with those of 5-anti). 31P{1H} NMR (C6D6): δ 16.6
X-ray Crystallography. Single crystals of 2b 0.25C6H14, 5, 6
3
(sealed in glass capillaries under argon), and 70 (coated with
mineral oil) were mounted on a Rigaku Mercury-CCD diffract-
ometer equipped with a graphite-monochromatized Mo KR
1
(s with 195Pt satellites, JPt-P = 4235 Hz); the other satellite
peaks were too weak to be assigned. The ratio of 5-anti:5-syn was
ca. 10.
source. Diffraction studies were done at 20 °C for 2b 0.25C6H14,
3
Preparation of 2b. The reaction mixture containing 5 was
prepared as described above and then thoroughly degassed. The
reaction vessel was filled with CO (1 atm), and the mixture was
stirred overnight at room temperature. The resulting orange
solution was dried in vacuo, and the residue was crystallized
5, and 6 and at -160 °C for 70 by using CrystalClear program
package,17 whose details are listed in Table 3. All diffraction
data were corrected for absorption.
Structure solution and refinements were conducted by using
the CrystalStructure program package.18 The positions of non-
hydrogen atoms were determined by Patterson methods (PATTY)19
from benzene-hexane. The yield of 2b 0.25C6H14 as red crys-
3
tals was 62 mg (38% based on 1b). Anal. Calcd for C62.5H62.5
OP2Se2IrPt2: C, 46.00; H, 3.86. Found: C, 46.37; H, 3.53. For
-
(17) CrystalClear 1.3.5; Rigaku Corporation, 1999. CrystalClear Soft-
ware User’s Guide; Molecular Structure Corporation, 2000. Pflugrath J. W.
Acta Crystallogr. D 1999, 55, 1718.
(18) CrystalStructure 3.8.0: Crystal Structure Analysis Package; Rigaku
and Rigaku/MSC, 2000-2006. Carruthers, J. R.; Rollett, J. S.; Betteridge,
P. W.; Kinna, D.; Pearce, L.; Larsen, A.; Gabe, E. CRYSTALS Issue 11;
Chemical Crystallography Laboratory: Oxford, U.K., 1999.
(19) Beurskens, P. T.; Admiraal, G.; Beurskens, G.; Bosman, W. P.;
Garcia-Granda, S.; Gould, R. O.; Smits, J. M. M.; Smykall, C. PATTY,
The DIRDIF Program System; Technical Report of the Crystallography
Laboratory; University of Nijmegen: Nijmegen, The Netherlands, 1992.
(12) Han, L.-B.; Choi, N.; Tanaka, M. J. Am. Chem. Soc. 1997, 119,
1795.
(13) Arce, A. J.; Deeming, A. J.; De Sanctis, Y.; Machado, R.;
Manzur, J.; Rivas, C. J. Chem. Soc., Chem. Commun. 1990, 1568.
(14) Herberhold, M.; Jin, G.-X.; Rheingold, A. L. J. Organomet.
Chem. 1998, 570, 241.
(15) Ugo, R.; Cariati, F.; La Monica, G. Inorg. Synth. 1968, 11, 105.
(16) gNMR: Program for Simulation of One-Dimensional NMR
Spectra; Adept Scientific: Amor Way, U.K., 1995-1999.

Article
Organometallics, Vol. 29, No. 10, 2010 2259
Table 3. Crystal Data for 2b 0.25C6H14, 5, 6, and 70
3
2b 0.25C6H14
3
5
6
7’
formula
fw
C
62.5H62.5IrOP2Pt2Se2
1631.95
C60H59IrP2Pt2Se2
1582.39
triclinic
P1 (No. 2)
10.729(3)
13.475(4)
19.873(6)
80.076(10)
80.078(10)
78.17(1)
C43H44IrOPPtS2
1059.22
triclinic
P1 (No. 2)
9.187(2)
10.727(2)
20.867(3)
90.904(2)
91.274(2)
102.718(3)
C62H58IrOP2Pt2S2
1527.61
cryst syst
space group
triclinic
monoclinic
P21/n (No. 14)
11.2868(8)
40.900(2)
12.8571(8)
90
P1 (No. 2)
14.872(4)
18.127(4)
22.248(5)
96.423(3)
103.352(4)
95.387(3)
5754(2)
˚
a, A
˚
b, A
˚
c, A
R, deg
β, deg
γ, deg
114.5349(9)
90
3
˚
V, A
Z
2742(2)
2
1.92
2005.1(5)
2
1.75
5399.4(6)
4
1.88
4
1.88
dcalcd, g cm-3
cryst size, mm3
no. of unique reflns
no. of data with I>2σ(I)
no. of variables
transmn factor
0.20 ꢀ 0.13 ꢀ 0.13
25 998 (Rint = 0.070)
12 142
0.20 ꢀ 0.20 ꢀ 0.20
0.30 ꢀ 0.25 ꢀ 0.10
0.40 ꢀ 0.40 ꢀ 0.20
12 125 (Rint = 0.073)
10 940
12 051 (Rint = 0.046)
7523
663
8782 (Rint = 0.029)
6575
486
1329
675
0.159-0.331
0.064
0.193
0.094-0.168
0.056
0.158
1.006
P
0.262-0.498
0.030
0.103
1.014
P
0.137-0.210
0.055
0.144
a
R1
wR2
b
GOFc
1.050
1.357
P
P
P
a R1
=
||Fo| - |Fc||/ |Fo| (I > 2σ(I)). b wR2 = [ (w(Fo - Fc2)2)/ w(Fo2)2]1/2 (all data). c GOF = [ w(|Fo| - |Fc|)2/{(no. observed) -
2
(no. variables)}]1/2
.
and subsequent Fourier synthesis (DIRDIF99),20 which were
refined with anisotropic thermal parameters by full-matrix least-
squares techniques. Hydrogen atoms were placed at the calcu-
lated positions and included at the final stages of the refinements
with fixed parameters.
18065005, “Chemistry of Concerto Catalysis”) and in
part by the Global COE Program “Chemistry Innovation
through Cooperation of Science and Engineering” from
the Ministry of Education, Culture, Sports, Science and
Technology, Japan. JSPS Grant-in-Aid for Fellows (20-
6569) is also appreciated (T.N.).
Acknowledgment. This work was supported by a Grant-
in-Aid for Scientific Research on Priority Areas (No.
Supporting Information Available: Details of X-ray crystal-
lographic data in CIF format for 2b 0.25C6H14, 5, 6, and 70 and
additional experimental procedures. This material is available
free of charge via the Internet at http://pubs.acs.org.
(20) Beurskens, P. T.; Admiraal, G.; Beurskens, G.; Bosman, W. P.;
de Gelder, R.; Israel, R.; Smits, J. M. M. The DIRDIF-99 Program
System; Technical Report of the Crystallography Laboratory; University of
Nijmegen: Nijmegen, The Netherlands, 1999.
3