Syntheses of series of trinuclear MIr2 or pentanuclear MIr4 bimetallic bis(selenido) and selenido-sulfido clusters (M = Pd, Pt, Fe, Co) from diiridium μ-bis(hydroselenido) and μ-hydroselenido-hydrosulfido complexes [{(η5-C5Me5) IrCl}2(μ-SeH)(μ-EH)] (E = Se, S)

Article abstract of DOI:10.1016/S0022-328X(02)02226-X

Reactions of a diiridium μ-bis(hydroselenido) complex [Cp*IrCl(μ-SeH)2IrCp*Cl] (1a; Cp= η⁵-C₅Me₅) with [MCl₂(cod)] (M = Pd, Pt; cod = 1,5-cyclooctadiene), FeCl₂, and CoCl₂ readily afforded the bimetallic selenido clusters containing a trinuclear or a pentanuclear cores [(Cp*Ir)₂(MCl₂)(μ₃- Se)₂] (M = Pd, Pt (5), Fe (6)) and [(Cp*Ir)₄Co (μ₃-Se)₄][CoCl₃(MeCN)]₂ (8). Cluster 6 was converted to the latter-type bow-tie cluster complex [Cp*IrCl(μ-SeH)(μ-SH)IrCp*Cl] (3) was obtained by the reaction of [Cp*IrCl(μ-Cl)₂IrCp*Cl] with one equiv of H₂Se generated in situ from a NaSeH/HCl aq. mixture, followed by that with H₂S gas. Treatment of 3 with a range of transition metal compounds has shown that 3 can serve as a good precursor to synthesize a series of mixed-chalcogenido clusters in a rational manner; selenido-sulfido clusters derived from 3 include [(Cp*Ir)₂(MCl ₂) (μ₃-Se)(μ₃-S)] (M = Pd, Pt, Fe (14)), [(Cp*Ir)₂{PtCl(PPh₃)} (μ₃-Se)(μ₃-S)]Cl (13), [(Cp*Ir)₄Co (μ₃-Se)₂ (μ₃-S)₂][CoCl ₃(MeCN)]₂ (15), and [(Cp*Ir)₄Fe(μ₃-Se)₂ (μ₃-S)₂][BPh₄]₂. To determine the detailed structures, X-ray analyses have been undertaken for 5.1/ 2ClCH²CH²Cl, 6, 7, 8, 13·CH2Cl2, 14, and 15·CH2Cl2.

Full text of DOI:10.1016/S0022-328X(02)02226-X

Journal of Organometallic Chemistry 669 (2003) 124ꢀ134
/
www.elsevier.com/locate/jorganchem
Syntheses of a series of trinuclear MIr2 or pentanuclear MIr4 bimetallic
bis(selenido) and selenidoꢀsulfido clusters (MꢁPd, Pt, Fe, Co) from
diiridium m-bis(hydroselenido) and m-hydroselenidoꢀhydrosulfido
Se, S)
/
/
/
complexes [{(h5-C5Me5)IrCl}2(m-SeH)(m-EH)] (Eꢁ
/
Shoken Nagao a, Hidetake Seino a, Masanobu Hidai b, Yasushi Mizobe a,*
a Institute of Industrial Science, The University of Tokyo, Komaba, Meguro-ku, Tokyo 153-8505, Japan
b Department of Materials Science and Technology, Faculty of Industrial Science and Technology, Tokyo University of Science, Noda, Chiba 278-8510,
Japan
Received 25 November 2002; received in revised form 10 December 2002; accepted 26 December 2002
Abstract
Reactions of a diiridium m-bis(hydroselenido) complex [Cp*IrCl(m-SeH)2IrCp*Cl] (1a; Cp*ꢁ
Pd, Pt; codꢁ1,5-cyclooctadiene), FeCl2, and CoCl2 readily afforded the bimetallic selenido clusters containing a trinuclear or a
pentanuclear cores [(Cp*Ir)2(MCl2)(m3-Se)2] (MꢁPd, Pt (5), Fe (6)) and [(Cp*Ir)4Co(m3-Se)4][CoCl3(MeCN)]2 (8). Cluster 6 was
converted to the latter-type bow-tie cluster [(Cp*Ir)4Fe(m3-Se)4][BPh4]2 (7) by treatment with an additional amount of 1a and excess
NaBPh4. Novel m-hydroselenidoꢀhydrosulfido complex [Cp*IrCl(m-SeH)(m-SH)IrCp*Cl] (3) was obtained by the reaction of
/
h5-C5Me5) with [MCl2(cod)] (Mꢁ
/
/
/
/
[Cp*IrCl(m-Cl)2IrCp*Cl] with one equiv of H2Se generated in situ from a NaSeH/HCl aq. mixture, followed by that with H2S gas.
Treatment of 3 with a range of transition metal compounds has shown that 3 can serve as a good precursor to synthesize a series of
mixed-chalcogenido clusters in a rational manner; selenidoꢀ
(MꢁPd, Pt, Fe (14)), [(Cp*Ir)2{PtCl(PPh3)}(m3-Se)(m3-S)]Cl (13), [(Cp*Ir)4Co(m3-Se)2(m3-S)2][CoCl3(MeCN)]2 (15), and
[(Cp*Ir)4Fe(m3-Se)2(m3-S)2][BPh4]2. To determine the detailed structures, X-ray analyses have been undertaken for 5×1/
CH2Cl2.
/
sulfido clusters derived from 3 include [(Cp*Ir)2(MCl2)(m3-Se)(m3-S)]
/
/
2ClCH2CH2Cl, 6, 7, 8, 13×
/
CH2Cl2, 14, and 15×
/
# 2003 Elsevier Science B.V. All rights reserved.
Keywords: Bimetallic selenido clusters; Trinuclear and pentanuclear cores; Diiridium hydroselenido complexes
1. Introduction
core structures and atom compositions [1] have recently
been extended to those of the corresponding selenido
clusters. Thus, we have reported the syntheses of a
diiridium m-tetraselenido complex [Cp*Ir(m-Se4)2IrCp*]
Our extensive studies on the exploration of the
rational routes leading to the high-yield synthesis of
homo- and hetero-metallic sulfido clusters with desired
(Cp*ꢁ
nido complexes such as [Cp*MCl(m-SeH)2MCp*Cl]
(MꢁIr (1a), MꢁRh (1b)) [3] and [CymRuCl(m-
SeH)2RuCymCl] (Cymꢁp-cymene) [4], and these di-
/
h5-C5Me5) [2] along with dinuclear m-hydrosele-
/
/
/
* Corresponding author. Tel.: ꢂ
6361.
E-mail address: ymizobe@iis.u-tokyo.ac.jp (Y. Mizobe).
/
81-3-5452-6360; fax: ꢂ81-3-5452-
/
nuclear complexes have proved to serve as good
precursors to a range of new homo- and hetero-metallic
0022-328X/03/$ - see front matter # 2003 Elsevier Science B.V. All rights reserved.
doi:10.1016/S0022-328X(02)02226-X

S. Nagao et al. / Journal of Organometallic Chemistry 669 (2003) 124ꢀ
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125
clusters with m-selenido ligands. These include the
Ir2Pd2Se3 and Ir2Pd3Se5 clusters obtained from the
former iridium tetraselenido complex [2a] and the
cubane-type M4Se4 clusters (MꢁIr, Rh, Ru) derived
/
from the latter hydroselenido complexes [3,4].
Since our previous studies have already shown that
the m-hydrosulfido complexes [Cp*MCl(m-SH)2-
MCp*Cl] (2; MꢁRu, Ir, Rh) are quite versatile for
/
It is noteworthy that the reactions occur more smoothly
for 1a as compared to those of the hydrosulfido
analogue 2a. Thus, the reactions of 1a yielding 4 and 5
complete in several hours at room temperature, whereas
to convert all 2a cleanly into the corresponding sulfido
clusters higher reaction temperatures (e.g. 50 8C) were
required. Single-crystal X-ray analysis has been carried
out for 5 to confirm the structures of these products, the
results of which are shown in Fig. 1.
The reaction of 1a with an equimolar amount of
FeCl2 in THF at room temperature also gave a tri-
nuclear selenido cluster [(Cp*Ir)2(FeCl2)(m3-Se)2] (6) as
black crystals (Scheme 1). Subsequent treatment of
paramagnetic 6 with one equiv of 1a in the presence of
NaBPh4 in THF at room temperature resulted in the
formation of the diamagnetic pentanuclear complex
with a bow-tie core [(Cp*Ir)4Fe(m3-Se)4][BPh4]2 (7) as
red crystals (Scheme 1). Cluster 7 was also obtained by
reacting 6 with only NaBPh4, presumably via the
degradation of the Ir2Fe core of part of 6. Both 6 and
7 have been fully characterized by the X-ray analyses,
whose structures are depicted in Figs. 2 and 3, respec-
tively. Analogous reactions of 1a were also carried out
with CoCl2 and NiCl2, which showed that only the
preparing not only the cubane-type tetranuclear clusters
but also numerous trinuclear and pentanuclear sulfido
clusters [5], conversion of 1a, which is the selenium
analogue of 2a (MꢁIr), into the bimetallic selenido
/
clusters with triangular cores or pentanuclear bow-tie
cores has been investigated in this study. Furthermore,
we have succeeded in preparing a new diiridium complex
having both the hydroselenido and hydrosulfido ligands
[Cp*IrCl(m-SeH)(m-SH)IrCp*Cl] (3), which has proved
to be an excellent starting complex to obtain the mixed-
chalcogenido clusters containing both the selenido and
sulfido ligands. This represents one of the still rare
pathways leading to the formation of tailored mixed-
chalcogenido clusters and its details are also reported
herein.
2. Results and discussion
2.1. Reactions of 1a with transition metal compounds
As reported already, [Cp*MCl(m-SH)2MCp*Cl]
pentanuclear
cluster
[(Cp*Ir)4Co(m3-Se)4][CoCl3-
(MeCN)]2 (8) was isolable by treatment with the former,
the product(s) from 1a and NiCl2 being intractable.
Although the reaction of equimolar amounts of 1a and
(MꢁIr (2a), Rh (2b), Ru (2c)) readily react with various
/
metal compounds accompanied by dehydrochlorination
to give a trinuclear clusters with two capping sulfido
ligands, which are formulated as [(Cp*M)2(M?Lm)(m3-
S)2]n (e.g. Mꢁ
RuCl2(PPh3); Mꢁ
cyclooctadiene) [5c], FeCl2 [5d]; Mꢁ
/
Ir: M?Lm ꢁ
/
PdCl2, PdCl(PPh3) [5a],
Rh(cod) (codꢁ1,5-
Ru: M?Lm ꢁ
/
Ir, Rh: M?Lm ꢁ
/
/
/
/
RuCl(PPh3)2(m-H) [5e], RhCl2(PPh3)(m-H) [5f]; etc.). In
the preceding paper [3], we described the syntheses of the
Ir and Rh m-hydroselenido analogues 1 and the sub-
sequent transformations of the Rh complex 1b into
triangular Rh3(m3-Se)2 clusters such as [(Cp*Rh)2-
(RhL2)(m3-Se)2]ꢂ (Lꢁ
CO, PPh3) and [(Cp*Rh)3(m3-
/
Se)2]2ꢂ along with the condensation of two molecules
of 1 to afford the cubane-type tetranuclear clusters
[(Cp*M)4(m3-Se)4] (Mꢁ/Ir, Rh).
Now it has been found that the reactions of 1a with
one equiv of [PdCl2(cod)] or [PtCl2(cod)] in THF
proceed in an analogous manner to those of 2a to give
the trinuclear bimetallic selenido clusters [(Cp*Ir)2-
Fig. 1. An ORTEP drawing of 5. Thermal ellipsoids are drawn at the
50% probability level. Hydrogen atoms and solvating ClCH2CH2Cl
are omitted for clarity.
(MCl2)(m3-Se)2] (Mꢁ
/
Pd (4), Pt (5)) as green crystals
(Eq. (1)).

126
S. Nagao et al. / Journal of Organometallic Chemistry 669 (2003) 124ꢀ134
/
Scheme 1.
CoCl2 directly gave 8, the yield was quite low. However,
when treated with 1.5 equivalents of CoCl2 as required
from the Co:Ir ratio of 3:4 in 8, 1a was converted into 8
in satisfactory yield. These results on the reactions of 1a
with FeCl2 and CoCl2 are analogous to those of the
hydrosulfido complex 2a previously observed [5d]. By
contrast, although the NiIr4 sulfido cluster was also
available from 2a and NiCl2 under more forcing
condtions, somehow the corresponding Se cluster could
not be obtained from the reactions using 1a. Cluster 8
has been characterized by the X-ray analysis as depicted
in Fig. 4.
2.2. Synthesis of diiridium m-hydroselenidoꢀ/hydrosulfido
complex 3
Since the diiridium complexes with two bridging
hydrochalcogenido ligands 1a and 2a have turned out
to be quite excellent precursors to synthesize a variety of
chalcogenido clusters, attempts have been made to
prepare a diiridium mixed-hydrochalcogenido complex,
aiming at derivatizing mixed-chalcogenido clusters in a
rational manner.
Now we have found that when [Cp*IrCl(m-
Cl)2IrCp*Cl] (9) was treated with one equiv of H2Se,
which was generated in situ from one equiv of NaSeH
and 1.15 equivalents of HCl aq. in CH2Cl2 at 0 8C, a m-
hydoselenido complex [Cp*IrCl(m-SeH)(m-Cl)IrCp*Cl]
(10) was obtained as a major product (Scheme 2).
Fig. 2. An ORTEP drawing of 6. Thermal ellipsoids are drawn at the
50% probability level. Hydrogen atoms are omitted for clarity.
1
Thus, the H-NMR spectrum of the reaction mixture
Fig. 3. An ORTEP drawing of 7. Thermal ellipsoids are drawn at the
30% probability level. The anions and hydrogen atoms are omitted for
clarity.
Fig. 4. An ORTEP drawing of 8. Thermal ellipsoids are drawn at the
30% probability level. The anions and hydrogen atoms are omitted for
clarity.

S. Nagao et al. / Journal of Organometallic Chemistry 669 (2003) 124ꢀ
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127
bis(hydrosulfido) complex 2a. Furthermore, the differ-
ence in the chemical shifts of the two Cp* singlets due to
the predominant isomer of 3 (0.21 ppm), which is much
larger than that of the minor isomer (0.04 ppm), is in
good agreement with those observed for the syn isomers
of both 1a (0.19 ppm) [3] and 2a (0.23 ppm) [5c,6]. These
data might suggest that the predominant form in
solution might be assignable to be syn also for 3.
2.3. Syntheses of mixed-metal mixed-chalcogenido
clusters
Reactions of 3 with a range of transition metal
compounds were carried out in an analogous manner
to those of 1a. Thus, when 3 was allowed to react with
Scheme 2.
showed the presence of 10, bis(hydroselenido) complex
1a, and the unreacted 9 in a ratio of 18:1:1, indicating
clearly that the initial replacement of the Cl ligand in 9
forming 10 is much faster than the following substitu-
tion reaction converting 10 into 1a at room temperature.
By contrast, treatment of 9 under similar conditions
with one equiv of H2S generated analogously from
NaSH and HCl aq. has resulted in the formation of a
mixture containing [Cp*IrCl(m-SH)(m-Cl)IrCp*Cl],
bis(hydrosulfido) complex 2a, and the unreacted 9 in a
ratio of 2:1:1.
one equiv of [MCl2(cod)] (Mꢁ
selenidoꢀsulfido clusters [(Cp*Ir)2(MCl2)(m3-Se)(m3-S)]
(MꢁPd (11), Pt (12)) were obtained as green crystals in
/Pd, Pt), expected
/
/
moderate yields. Cluster 12 was further reacted with an
equimolar amount of PPh3 to afford a cationic cluster
[(Cp*Ir)2{PtCl(PPh3)}(m3-Se)(m3-S)]Cl (13) (Scheme 3),
whose structure was determined unequivocally by the X-
ray analysis (Fig. 5). Despite the use of a starting
complex 3 contaminated with 1a and 2a, these products
1
are pure from the H-NMR criteria and the elemental
analyses also gave the satisfactory results.
Since the isolation of 10 in pure form was unsuccess-
ful, the resultant reaction mixture containing 10 as the
major component was successively treated with an
excess of H2S gas at 0 8C, which afforded a mixture
containing the desired mixed-hydrochalcogenido com-
plex 3 (90%) along with impurities 1a (5%) and 2a (5%)
(Scheme 2). This result indicates that the replacement of
the m-SeH ligand by the SH anion does not take place
under these conditions. Attempts to isolate analytically
pure 3 were unsuccessful, the following syntheses of the
mixed chalcogenido clusters were conducted by the use
of this product without further purification.
Complex 3 also reacted with FeCl2 and CoCl2 under
the conditions essentially analogous to those for pre-
paring 6 and 8 from 1a, yielding paramagnetic
[(Cp*Ir)2(FeCl2)(m3-Se)(m3-S)] (14) and [(Cp*Ir)4Co(m3-
Se)2(m3-S)2][CoCl3(MeCN)]2 (15), respectively. The for-
mer was convertible to an expected diamagnetic bow-tie
As observed previously for the precedented m-hydro-
1
selenido and m-hydrosulfido complexes 1 and 2, the H-
NMR spectrum showed that 3 exists as a mixture of syn
Scheme 3.
and anti forms with respect to the two m-EH (Eꢁ
/S, Se)
groups in solution (Eq. (2)).Thus, previous work has
shown that both 1a and 2a are present in C6D6 at room
temperature as a mixture of the syn and anti forms in a
ratio of 3:2, which was easily determined on the basis of
the intensity ratio of the Cp* resonances assignable to
these two isomers: two singlets with the same intensities
for the syn isomers and one singlet for the anti isomers.
By contrast, for 3 both the syn and anti forms contain
two inequivalent Cp* groups and show two Cp*
resonances. Hence, the signals due to the two isomers
are unable to be assigned unambiguously. However, also
for the hydroselenidoꢀhydrosulfido complex 3, two sets
of the Cp* signals appeared in an intensity ratio of 3:2 as
observed for the bis(hydroselenido) complex 1a and the
/
Fig. 5. An ORTEP drawing of 13. Thermal ellipsoids are drawn at the
50% probability level. Hydrogen atoms and solvating CH2Cl2 are
omitted for clarity.

128
S. Nagao et al. / Journal of Organometallic Chemistry 669 (2003) 124ꢀ134
/
Fig. 6. An ORTEP drawing of 14. Thermal ellipsoids are drawn at the
50% probability level. Hydrogen atoms are omitted for clarity.
Fig. 7. An ORTEP drawing of 15. Thermal ellipsoids are drawn at the
30% probability level. The anions and hydrogen atoms along with
solvating CH2Cl2 are omitted for clarity.
cluster [(Cp*Ir)4Fe(m3-Se)2(m3-S)2][BPh4]2 (16) similarly
(Scheme 4). In the FAB-MS spectrum of 14, the peak
assignable to the ion [14ꢃ
Cl]ꢂ appeared, whereby those
arising from the bis(selenido) and bis(sulfido) analogues
/
using the m-hydroselenidoꢀ
reported here may therefore represent quite a powerful
method to obtain mixed selenidoꢀsulfido clusters nu-
merously. Reactivities of new selenidoꢀsulfido clusters
/hydrosulfido complex 3
of 14 were not detectable. This also indicates that only
/
the selenidoꢀsulfido cluster 14 was isolated in a pure
/
/
form. Clusters 14 and 15 have been characterized by the
X-ray diffraction as shown in Figs. 6 and 7.
are now under investigation and the results will be
described elsewhere.
Reactivities displayed at the multinuclear metalꢀ
/
sulfido sites and their selenido analogues are currently
attracting increasing interest in relevance to certain
biological and industrial catalysis, and the mixed-
chalcogenido clusters are of considerable importance
because of their potential as good models to clarify the
site selectivity exhibited at the multimetallic mixed-
chalcogenido site. However, although a range of
2.4. Description of the X-ray structures of bis(selenido)
and selenidoꢀsulfido clusters
/
The X-ray analyses have been carried out to deter-
mine the detailed structures for diselenido clusters 5, 6, 7
and 8 as well as selenidoꢀ
Pertinent bonding parameters in these clusters are listed
in Tables 1ꢀ7, respectively.
As shown in Fig. 1, 5 has a triangular core, for which
/sulfido clusters 13, 14 and 15.
sulfidoꢀ
ido clusters are known, which include, for example,
those derived from [Fe2(m-EE?)(CO)6] (E, E?ꢁS, Se, Te)
/
selenido, sulfidoꢀ
/
telurido, and selenidoꢀtelur-
/
/
/
˚
[7], well-defined mixed-chalcogenido clusters are still
rare and little is known about the methods to prepare
such clusters in a reliable manner [8]. The reactions
the Irꢀ
at 2.751(1) A fall in the range of the metalꢀ
bond lengths, whereas the remaining Ptꢀ
/
Ir distance at 2.913(1) A and one Ptꢀ
/
Ir distance
˚
/metal single
/Ir distance is
Scheme 4.

S. Nagao et al. / Journal of Organometallic Chemistry 669 (2003) 124ꢀ
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129
Table 1
Table 3
˚
˚
Selected bond lengths (A) and bond angles (8) in 5
Selected bond lengths (A) and bond angles (8) in 7
Bond lengths
Bond lengths
Ptꢀ
Ir(1)ꢀ
/
Ir(1)
Ir(2)
2.751(1)
2.913(1)
2.408(2)
2.352(5)
2.435(2)
2.413(2)
Ptꢀ ꢀ ꢀIr(2)
3.487(1)
2.411(2)
2.366(5)
2.424(2)
2.410(2)
Feꢀ
/
Ir(1)
2.742(2)
2.770(3)
2.8121(9)
2.279(3)
2.280(3)
2.394(2)
2.393(2)
2.394(2)
2.404(2)
Feꢀ
/
Ir(2)
Ir(4)
2.759(3)
/
Ptꢀ/Se(2)
Feꢀ
/
Ir(3)
Feꢀ
/
2.758(2)
2.799(1)
2.282(3)
2.274(3)
2.395(2)
2.398(2)
2.403(2)
2.383(2)
Ptꢀ
/
Se(1)
Cl(1)
Ptꢀ/Cl(2)
Ir(1)ꢀ
/Ir(2)
Ir(3)ꢀIr(4)
/
Ptꢀ
/
Ir(1)ꢀ/Se(2)
Feꢀ
/
Se(1)
Feꢀ
/
Se(2)
Se(4)
Ir(1)ꢀ
Ir(2)ꢀ
/
Se(1)
Se(1)
Ir(2)ꢀ/Se(2)
Feꢀ
/
Se(3)
Feꢀ
/
/
Ir(1)ꢀ
Ir(2)ꢀ
Ir(3)ꢀ
Ir(4)ꢀ
/
Se(1)
Se(1)
Se(3)
Se(3)
Ir(1)ꢀ
Ir(2)ꢀ
Ir(3)ꢀ
Ir(4)ꢀ
/
Se(2)
Se(2)
Se(4)
Se(4)
/
/
Bond angles
PtꢀIr(1)ꢀIr(2)
Se(1)ꢀPtꢀ
Se(1)ꢀPtꢀ
Se(2)ꢀPtꢀ
Se(1)ꢀ
PtꢀSe(1)ꢀ
Ir(1)ꢀSe(1)ꢀ
PtꢀSe(2)ꢀIr(2)
/
/
/
/
75.94(3)
83.99(7)
92.5(1)
Se(1)ꢀ
Se(2)ꢀ
Cl(1)ꢀ
Se(1)ꢀ
PtꢀSe(1)ꢀ
PtꢀSe(2)ꢀ
Ir(1)ꢀ
/
Ptꢀ
Ptꢀ
Ptꢀ
/
Cl(1)
Cl(1)
Cl(2)
175.1(2)
91.1(2)
92.4(2)
/
/
/
/
Se(2)
Cl(2)
Cl(2)
/
/
/
/
/
/
Bond angles
/
/
172.6(2)
83.12(6)
69.21(5)
73.84(5)
92.65(7)
/Ir(2)ꢀ
/
Se(2)
83.88(7)
92.64(7)
69.36(5)
74.09(5)
Ir(1)ꢀ
FeꢀIr(2)ꢀ
Se(1)ꢀFeꢀ
Se(2)ꢀFeꢀ
Se(3)ꢀFeꢀ
Se(1)ꢀ
Se(3)ꢀ
FeꢀSe(1)ꢀ
FeꢀSe(2)ꢀ
Ir(1)ꢀ
FeꢀSe(3)ꢀ
FeꢀSe(4)ꢀ
Ir(3)ꢀ
/Feꢀ
/
Ir(2)
61.49(5)
58.95(5)
127.2(1)
105.0(1)
98.5(1)
Feꢀ
Se(1)ꢀ
Se(1)ꢀ
Se(2)ꢀ
Se(1)ꢀ
Se(3)ꢀ
FeꢀSe(1)ꢀ
Ir(1)ꢀSe(1)ꢀ
FeꢀSe(2)ꢀ
FeꢀSe(3)ꢀ
Ir(3)ꢀ
FeꢀSe(4)ꢀ
/
Ir(1)ꢀ
Feꢀ
Feꢀ
Feꢀ
/
Ir(2)
59.57(5)
98.6(1)
/
Ir(1)ꢀ
Ir(1)
Ir(2)
/
Se(2)
/
/Ir(2)
/
/
Ir(1)
/
/
Se(2)
Se(4)
Se(4)
/
/
/
/Ir(1)
/
/
Se(3)
Se(3)
Se(4)
/
/
104.2(1)
126.3(1)
92.46(6)
92.01(7)
71.80(8)
71.95(6)
72.21(8)
72.64(8)
71.37(5)
72.57(8)
/
/
/Se(2)ꢀ
/
Ir(2)
/
/
/
/
/
/
/
/
/Ir(1)ꢀ
/
Se(2)
Se(4)
/
Ir(2)ꢀ
/Se(2)
92.41(7)
92.25(7)
72.36(8)
71.72(8)
71.84(5)
72.10(8)
72.56(8)
71.56(5)
/Ir(3)ꢀ
/
/
Ir(4)ꢀ
/Se(4)
/
/Ir(1)
/
/Ir(2)
/
/
Ir(2)
/
/Ir(1)
/
/Ir(2)
/Se(2)ꢀ
/Ir(2)
/
/Ir(3)
Table 2
˚
/
/Ir(4)
/Se(3)ꢀ
/
Ir(4)
Selected bond lengths (A) and bond angles (8) in 6
/
/Ir(3)
/
/Ir(4)
Bond lengths
/Se(4)ꢀIr(4)
/
Feꢀ
Ir(1)ꢀ
/
Ir(1)
2.926(2)
2.8520(6)
2.455(2)
2.230(5)
2.425(1)
2.415(1)
Feꢀ ꢀ ꢀIr(2)
3.120(2)
2.444(2)
2.252(4)
2.422(1)
2.413(1)
/
Ir(2)
Feꢀ
/
Se(2)
Feꢀ
/
Se(1)
Feꢀ/Cl(2)
Table 4
Feꢀ
/
Cl(1)
Ir(1)ꢀ/Se(2)
˚
Selected bond lengths (A) and bond angles (8) in 8
Ir(1)ꢀ
Ir(2)ꢀ
/
Se(1)
Se(1)
Ir(2)ꢀ/Se(2)
/
Bond lengths
Bond angles
FeꢀIr(1)ꢀIr(2)
Se(1)ꢀFeꢀ
Se(1)ꢀFeꢀ
Se(2)ꢀFeꢀ
Se(1)ꢀ
FeꢀSe(1)ꢀ
Ir(1)ꢀSe(1)ꢀ
FeꢀSe(2)ꢀIr(2)
Co(1)ꢀ
Ir(1)ꢀIr(2)
Co(1)ꢀSe(1)
/Ir(1)
2.913(1)
2.873(1)
2.302(3)
2.395(2)
2.415(2)
Co(1)ꢀ
/
Ir(2)
2.804(1)
2.293(3)
2.422(2)
2.397(2)
/
/
65.35(4)
89.14(6)
110.4(1)
114.6(1)
90.39(4)
73.68(5)
72.22(4)
79.92(6)
Se(1)ꢀ
Se(2)ꢀ
Cl(1)ꢀ
Se(1)ꢀ
FeꢀSe(1)ꢀ
FeꢀSe(2)ꢀ
Ir(1)ꢀ
/
Feꢀ
Feꢀ
Feꢀ
/
Cl(1)
Cl(1)
Cl(2)
120.1(2)
114.2(1)
107.9(2)
90.84(4)
79.68(5)
73.92(5)
72.30(3)
/
Co(1)ꢀ
/
Se(2)
/
/
Se(2)
Cl(2)
Cl(2)
/
/
/
Ir(1)ꢀ/Se(2)
/
/
/
/
Ir(1)ꢀ/Se(1)
Ir(2)ꢀ/Se(2)
/
/
/Ir(2)ꢀ
/
Se(2)
Ir(2)ꢀ/Se(1)
/
Ir(1)ꢀ
Ir(1)
Ir(2)
/Se(2)
/
/
Ir(2)
Ir(1)
Bond angles
Ir(1)ꢀCo(1)ꢀ
Co(1)ꢀIr(2)ꢀ
Se(1)ꢀCo(1)ꢀ
Se(1)ꢀCo(1)ꢀ
Se(1)ꢀIr(1)ꢀ
Co(1)ꢀSe(1)ꢀ
Ir(1)ꢀSe(1)ꢀIr(2)
Co(1)ꢀSe(2)ꢀIr(2)
/
/
/
/
/
/
Ir(2)
Ir(1)
60.30(2) Co(1)ꢀ
61.74(4) Se(1)ꢀCo(1)ꢀ
95.19(8) Se(2)ꢀCo(1)ꢀ
143.48(7) Se(1)ꢀIr(2)ꢀ
89.55(7) Co(1)ꢀSe(1)ꢀ
76.65(8) Co(1)ꢀSe(2)ꢀ
73.36(6) Ir(1)ꢀSe(2)ꢀ
73.38(8)
/
Ir(1)ꢀ
/
Ir(2)
57.96(4)
95.7(2)
96.4(2)
/
/
/
Se(2)ꢀ
/
Ir(2)
/
/
/
/Se(1*)
/
/
/
/Se(2)
/
/Se(2*)
/
/Se(2*)
/
/
Se(2)
89.66(7)
72.90(6)
76.27(6)
73.19(6)
/
/
Se(2)
/
/Ir(2)
˚
/
/Ir(1)
/
/Ir(1)
elongated to a non-bonding one at 3.487(1) A. Thus, the
PtIr2Se2 core has rather a square pyramidal structure
with the Ir(1) atom at the apex than a trigonal
bipyramid with two apical Se atoms. Analogous square
pyramidal cores have been demonstrated for the M3Se2
/
/
/
/
Ir(2)
/
/
The Irꢀ
same (2.410(2)ꢀ
IrꢀS bond distances in 17 (2.280(5)ꢀ
expected from the difference in the single-bond covalent
/
Se bond lengths in 5 and 6 are essentailly the
˚
clusters of e.g. Mꢁ
/Fe, Ru [9]. Inequivalency was also
/
2.435(2) A), which are longer than the
˚
2.328(6) A) as
observed for the two Feꢀ
/Ir distances in 6 (2.926(2) and
/
/
˚
3.120(2) A) but apparently the difference is much
smaller than that in 5, and the geometry of the FeIr2Se2
core in 6 is close to a trigonal bypyramid as depicted in
˚
˚
radius of Se at 1.17 A and that of S at 1.04 A [10]. For
comparison, the Ir(III)ꢀSe distances in the selenido
clusters reported previously are, e.g. 2.402(1)ꢀ
/
Fig. 2. It is also noteworthy that both of the two FeꢀIr
bonds are longer than the IrꢀIr bond at 2.8520(6) A,
indicating the weaker interactions present between Fe
and Ir atoms. In the related sulfido cluster
/
/
2.409(2)
˚
˚
˚
/
A in [(Cp*Ir)3(m3-Se)2][PF6]2 [3] and 2.482(2)ꢀ
/
2.501(2) A
in [(Cp*Ir)4(m3-Se)4] [11]. The Pt in 5 and the Fe in 6 are
each bonded to two Cl anions, and if the metalꢀmetal
/
[(Cp*Ir)2(FeCl)2(m3-S)2] (17) [5d], the Feꢀ
/
Ir distances
bonds are ignored, the geometry around the Pt is
essentially square planar, while that around the Fe is
˚
are 2.880(3) and 3.006(3) A, displaying the comparable
inequivalency but both being slightly shorter than those
in the selenido cluster 6.
almost tetrahedral. The Ptꢀ
/Se bond lengths in 5 are
˚
2.408(2) and 2.411(2) A, which are shorter than the Feꢀ
/

130
S. Nagao et al. / Journal of Organometallic Chemistry 669 (2003) 124ꢀ134
/
Table 5
Table 7
˚
˚
Selected bond lengths (A) and bond angles (8) in 13
Selected bond lengths (A) and bond angles (8) in 15
Bond lengths
Bond lengths
Ptꢀ
Ptꢀ
Ptꢀ
Irꢀ
/
Ir
3.041(1)
2.470(1)
2.351(3)
2.347(2)
Irꢀ
Ptꢀ
Ptꢀ
/
Ir*
2.935(1)
2.350(2)
2.262(3)
Co(1)ꢀ
Co(1)ꢀ
Ir(1)ꢀ
Co(1)ꢀ
Co(1)ꢀ
/
Ir(1)
2.796(2)
2.803(2)
2.840(1)
2.274(2)
2.275(2)
2.375(2)
2.367(2)
2.390(2)
2.360(2)
Co(1)ꢀ
Co(1)ꢀ
Ir(3)ꢀ
Co(1)ꢀ
Co(1)ꢀ
/
Ir(2)
Ir(4)
2.755(2)
2.773(2)
2.825(1)
2.287(2)
2.282(2)
2.375(2)
2.394(2)
2.373(2)
2.387(2)
/
Se
Cl
/S
/Ir(3)
/
/
/P
/
Ir(2)
/
Ir(4)
/
S
/E(1)
/
E(2)
E(4)
/E(3)
/
Bond angles
IrꢀPtꢀIr*
SeꢀPtꢀ
SeꢀPtꢀ
SꢀPtꢀ
SeꢀIrꢀ
PtꢀSeꢀ
PtꢀSꢀIr
Ir(1)ꢀ
Ir(2)ꢀ
Ir(3)ꢀ
Ir(4)ꢀ
/
E(1)
E(1)
E(3)
E(3)
Ir(1)ꢀ
Ir(2)ꢀ
Ir(3)ꢀ
Ir(4)ꢀ
/
E(2)
E(2)
E(4)
E(4)
/
/
57.71(2)
85.99(7)
179.40(9)
93.41(9)
87.30(5)
76.97(4)
80.70(7)
Ptꢀ
Seꢀ
SꢀPtꢀ
ClꢀPtꢀ
IrꢀSeꢀIr*
IrꢀSꢀIr*
/
Irꢀ
Ptꢀ
Cl
/
Ir*
61.15(1)
90.63(9)
176.6(1)
90.0(1)
/
/
/
/
S
/
/
Cl
/
/
/
/P
/
/
/
/
/
/
P
/
/
P
/
/
S
/
/
74.80(4)
77.40(7)
Bond angles
Ir(1)ꢀCo(1)ꢀ
Co(1)ꢀIr(2)ꢀ
Co(1)ꢀIr(3)ꢀ
E(1)ꢀCo(1)ꢀ
E(1)ꢀCo(1)ꢀ
E(2)ꢀCo(1)ꢀ
E(1)ꢀ
E(3)ꢀ
Co(1)ꢀ
Ir(1)ꢀE(1)ꢀ
Co(1)ꢀ
Co(1)ꢀ
Ir(3)ꢀE(3)ꢀ
Co(1)ꢀE(4)ꢀ
/
/Ir
/
/
/
/
Ir(2)
Ir(1)
Ir(4)
61.54(4) Co(1)ꢀ
59.95(4) Ir(3)ꢀCo(1)ꢀ
59.03(4) Co(1)ꢀIr(4)ꢀ
96.39(8) E(1)ꢀCo(1)ꢀ
131.1(1) E(2)ꢀCo(1)ꢀ
104.96(9) E(3)ꢀCo(1)ꢀ
91.39(7) E(1)ꢀ
90.73(7) E(3)ꢀ
73.91(7) Co(1)ꢀ
73.57(6) Co(1)ꢀ
72.07(7) Ir(1)ꢀE(2)ꢀ
73.82(7) Co(1)ꢀE(3)ꢀ
73.00(6) Co(1)ꢀE(4)ꢀ
72.98(7) Ir(3)ꢀE(4)ꢀIr(4)
/
Ir(1)ꢀ
/
Ir(2)
Ir(4)
Ir(3)
58.51(4)
60.89(4)
60.09(4)
103.70(9)
129.07(9)
96.09(9)
91.13(7)
91.33(7)
72.78(7)
73.70(7)
73.11(6)
73.45(7)
74.02(7)
72.97(6)
/
/
/
/
/
/
/
/
/
/
/
/
E(2)
E(4)
E(4)
/
/
E(3)
E(3)
E(4)
/
/
/
/
Table 6
/
/
/
/
˚
Selected bond lengths (A) and bond angles (8) in 14
/Ir(1)ꢀ
/
E(2)
/Ir(2)ꢀ
/
E(2)
/Ir(3)ꢀ
/
E(4)
/Ir(4)ꢀ
/
E(4)
Bond lengths
/
E(1)ꢀ
/Ir(1)
/
E(1)ꢀ
E(2)ꢀ
Ir(2)
Ir(4)
Ir(3)
/
Ir(2)
Feꢀ
Ir(1)ꢀ
Feꢀ
Feꢀ
Ir(1)ꢀ
Ir(2)ꢀ
/Ir(1)
2.898(1)
2.826(1)
2.414(2)
2.227(3)
2.399(1)
2.386(1)
Feꢀ ꢀ ꢀIr(2)
3.056(1)
/
/
Ir(2)
/
/
Ir(1)
/
Ir(2)
Feꢀ
/E(2)
2.398(2)
2.251(3)
2.376(1)
2.364(1)
/
E(2)ꢀ
E(3)ꢀ
Ir(4)
Ir(4)
/Ir(2)
/
/
/E(1)
Feꢀ
Ir(1)ꢀ
Ir(2)ꢀ
/Cl(2)
/
/Ir(3)
/
/
/Cl(1)
/E(2)
/
/
/
/
/
E(1)
E(1)
/E(2)
/
/
/
/
/
Bond angles
FeꢀIr(1)ꢀIr(2)
E(1)ꢀFeꢀ
E(1)ꢀFeꢀ
E(2)ꢀFeꢀ
E(1)ꢀ
FeꢀE(1)ꢀ
Ir(1)ꢀE(1)ꢀ
FeꢀE(2)ꢀIr(2)
˚
2.332(2)ꢀ
2.309(1) and 2.310(1) A in [RuCo2(m3-Se)(CO)7(m-
Ph2PCH2PPh2)] [17]. For comparison, the FeꢀS dis-
tances in [(Cp*Ir)4Fe(m3-S)4][BPh4]2 (18) are in the range
/
2.350(2) A for [Co6(m3Se)8(CO)6] [16] and
/
/
64.52(4)
89.05(6)
110.69(9)
115.63(9)
89.90(4)
74.03(4)
72.40(4)
79.84(5)
E(1)ꢀ
E(2)ꢀ
Cl(1)ꢀ
E(1)ꢀIr(2)ꢀ
FeꢀE(1)ꢀ
FeꢀE(2)ꢀ
Ir(1)ꢀ
/
Feꢀ
Feꢀ
Feꢀ
/
Cl(1)
120.0(1)
113.3(1)
107.6(1)
90.52(4)
79.09(5)
74.75(5)
73.19(4)
˚
/
/E(2)
/
/Cl(1)
/
/
/Cl(2)
/
/
Cl(2)
E(2)
/
/Cl(2)
/
/
/
Ir(1)ꢀ
Ir(1)
Ir(2)
/
E(2)
/
/Ir(2)
˚
A
2.161(4)ꢀ
/
2.171(4)
and the Coꢀ/S distances in
/
/
/
/Ir(1)
[(Cp*Ir)4Co(m3-S)4][CoCl3(MeCN)]2 (19) are 2.166(6)
and 2.183(5) A with the IrꢀS distances from 2.266(3)
to 2.298(5) A [5d]. It is noteworthy that the dihedral
angles between two MIr2 planes differ significantly for
/
/
/
E(2)ꢀ
/Ir(2)
˚
/
/
/
˚
˚
Se bond distances in 6 at 2.444(2) and 2.455(2) A. For
MꢁFe and Co, the former in 7 being 72.18 with the
/
latter in 8 of 49.08. This feature was also observed
previously for the sulfido analogues, whereby the
corresponding dihedral angles were found to be 73.4,
49.9, and 24.38 for 18, 19 and [(Cp*Ir)4Ni(m3-
comparison, the Ptꢀ
/
Se bond distances in the Pt(II)3
cluster [{Pt(PPh3)2}2{Pt(cod)}(m3-Se)2][PF6]2 are in the
˚
2.474(1) A [12] and those in the Pt(II)2
range 2.431(1)ꢀ
/
complex [{Pt(PPh3)}2(m2-Se)2] are 2.433(1) and 2.465(1)
S)4][NiCl4]×
/CH2Cl2 [5d], respectively, the former two
˚
A [13], all being slightly longer than those in 5. The Feꢀ
/
being in good agreement with those in the Se analogues
6 and 7. The previous finding for the latter sulfido
clusters was able to be interpreted to some extent in
terms of the valence electron counts and molecular
orbital calculations of these clusters [5d]. However,
more recent results on the X-ray analysis of
Se bond distances in the selenido clusters containing
˚
2.326(3) A for
lower valent Fe centers are e.g. 2.318(3)ꢀ
[(Ph3P)2N]2[Fe3(m3-Se)(CO)9] [14] and 2.34(2)ꢀ
for [Fe3(m3-Se)2(CO)9] [15].
In the pentanuclear bow-tie clusters 7 and 8, the Mꢀ
distances (MꢁFe, Co, Ir) in the range 2.742(2)ꢀ
2.913(1) A are all indicative of the presence of metalꢀ
metal bonding interactions between these atoms. The
IrꢀSe bond lengths in these two vary from 2.383(2) to
2.422(2) A. The Feꢀ
/
˚
/
2.37(2) A
/Ir
/
/
[(Cp*Ir)4Co(m3-S)4][BPh4]2×/CH2Cl2 have implicated
˚
/
that the packing effect exerted by the nature of the
anion seems to be the important factor to determine
these dihedral angles [18] and further studies are needed
to rationalize these findings about the structures of a
/
˚
/
Se bond lengths in 7 from 2.274(3)
to 2.282(3) A are considerably shorter than those in the
trinuclear cluster 6, while the CoꢀSe bond lengths in
˚
series of metalꢀ
type.
The structure of m-selenidoꢀ
/
chalcogenido bow-tie clusters of this
/
79eꢃ 8 are 2.293(3) and 2.302(3) A, which are longer
only slightly than those in a 78eꢃ cluster 7. The Coꢀ
Se
bond lengths reported previously are, for example,
˚
/sulfido cluster has been
/
clarified unambiguously for 13. Thus, the X-ray struc-
ture of the cationic cluster 13 has a crystallographically

S. Nagao et al. / Journal of Organometallic Chemistry 669 (2003) 124ꢀ
/134
131
imposed mirror plane defined by a square planar Pt
atom together with the Se, S, P, and Cl atoms, which
(MꢁPd, Pt) [20] were prepared according to the
literature methods.
/
bisects the Irꢀ
/
Ir* bond. The Ptꢀ
/
Ir and IrꢀIr* bond
/
˚
distances are 3.041(1) and 2.935(1) A, respectively. We
have previously observed the analogous X-ray structure
for the PdIr2S2 analogue [(Cp*Ir)2{PdCl(PPh3)}(m3-
3.2. Preparation of 3
Ethanol (3.0 cm3) was slowly added to gray Se (80 mg,
1.0 mmol) and NaBH4 (38 mg, 1.0 mmol) at 0 8C and
the mixture was stirred for 1 h at room temperature
(r.t.). The resultant mixture was dried up in vacuo and
to the residue were added a CH2Cl2 solution (40 cm3) of
9 (0.80 g, 1.0 mmol) and then concentrated HCl aq. (120
mg, 1.15 mol) at 0 8C. After stirring for 1 h at this
temperature, the resulting solution was dried over
MgSO4. The 1H-NMR spectrum of this mixture showed
the formation of mono(hydroselenido) complex 10 in
90% yield along with a byproduct 1a (5%). Unreacted 9
(5%) was also detected. The solution was separated from
MgSO4 and then treated with H2S gas at 0 8C for 5 min.
The mixture was evaporated to dryness in vacuo and the
residue was washed with acetone and hexane. The
yellow solid remained, which contained 3 with a purity
of 90% (0.50 g, 60% yield). 1H-NMR (C6D6, ppm):
isomer i, 1.51, 1.30 (s, 15H each, Cp*), 1.12 (s, 1H, SH),
S)2]Cl (20) with the Pdꢀ
/
Ir and IrꢀIr* bond lengths at
/
3.001(1) and 2.9002(9) [5a]. This core structure of 13 is
quite different from that of the neutral PtIr2Se2 cluster 5,
in which two PtꢀIr distances are apparently unequal
/
˚
with the separations of 2.751(1) and 3.487(1) A (vide
supra). It is to be noted, however, that even for 5, the
1H-NMR spectrum in CDCl3 at room temperature
shows only one singlet due to the Cp* protons,
indicating that two Ir centers become equivalent at
this temperature in the NMR time scale.
The X-ray structure of 13 clearly shows that the Cl
anion trans to the Se atom in 5 is selectively substituted
by PPh3, reflecting the stronger trans effect exerted by
Se2ꢃ than S2ꢃ bound to the Pt(II) center. The Ptꢀ
/Se
bond length at 2.470(1) is longer than those in 5
˚
(2.408(2) and 2.411(2) A), while the PtꢀS distance at
/
˚
2.350(2) A is comparable to those in [(Cp*Ir)2{Pt(dp-
˚
pe)}(m3-S)2][BPh4]2 (2.362(5) and 2.347(4) A) [5a].
For 14 and 15, the X-ray analyses have also disclosed
the presence of the expected trinuclear and pentanuclear
ꢀ
/
2.47 (s, 1H, SeH); isomer ii, 1.43, 1.39 (s, 15H each,
Cp*), 1.23 (s, 1H, SH), ꢃ2.37 (s, 1H, SeH); the ratio of
isomers i and ii is 3:2. Two isomers i and ii may be
assigned as syn and anti forms, respectively (see text).
/
core structures. Thus, the Feꢀ
/
Ir(1) and FeꢀIr(2) dis-
/
˚
tances in 14 at 2.898(1) and 3.056(1) A, respectively, are
inequivalent. This feature and these distances are
analogous to those in the bis(selenido) cluster 6 and
the bis(sulfido) cluster 17 shown above. On the other
3.3. Preparation of 4
A solution containing 1a (0.44 g, 0.50 mmol) and
[PdCl2(cod)] (0.14 g, 0.50 mmol) in THF (10 cm3) was
stirred at r.t. for 5 h. The green suspension was
evaporated to dryness in vacuo and the residue was
extracted with CH2Cl2. Addition of ether to the
concentrated extract afforded 4 as green crystals
(0.44g, 89% yield). Anal. Calc. for C20H30Cl2Ir2PdSe2:
C, 24.26; H, 3.05. Found: C, 24.44; H, 3.25%. 1H-NMR
(CDCl3, ppm): 2.10 (s, Cp*).
hand, the Coꢀ
2.755(2)ꢀ2.803(2) A. For comparison, the Coꢀ
lengths in the bis(selenido) cluster 8 are 2.804(1) and
/
Ir bond lengths in 15 are in the range
˚
/
/Ir bond
˚
2.913(1) A, while those in the bis(sulfido) cluster 19 are
˚
2.746(1) and 2.849(1) A. The dihedral angle between two
CoIr2 planes is 68.28. In 14 and 15, since the selenido
and sulfido ligands are mutually disordered with the
occupancy factor of 0.5, the bonding parameters asso-
ciated with the chalcogenido ligands are not discussed
here.
3.4. Preparation of 5
This complex was obtained from 1a (0.45 g, 0.50
mmol) and [PtCl2(cod)] (0.19 g, 0.50 mmol) by the same
method as that for 4 as green crystals in 46% yield (0.25
g). Anal. Calc. for C20H30Cl2Ir2PtSe2: C, 22.27; H, 2.80.
3. Experimental
1
3.1. General considerations
Found: C, 22.16; H, 3.00%. H-NMR (CDCl3, ppm):
2.10 (s, Cp*). Single crystals of 5×
the X-ray diffraction were available by recrystallization
from ClCH2CH2Clꢀether.
/
1/2ClCH2CH2Cl for
All manipulations were carried out under an atomo-
sphere of N2. IR and NMR spectra were recorded on
JASCO FT/IR 420 and JEOL AL-400 spectrometers,
respectively. The mass spectra were obtained by a JEOL
JMS600H spectrometer. Elemental analyses were per-
/
3.5. Preparation of 6
formed on a Perkinꢀ
zer. Chemicals were commercially obtained and used as
received, while compounds 1a [3], 9 [19], [MCl2(cod)]
/
Elmer 2400 Series II CHN analy-
This complex was obtained as black crystals in 54%
yield (50 mg) from 1a (87 mg, 0.098 mmol) and FeCl2
(13 mg, 0.10 mmol) in THF (3 cm3) by the same method

132
S. Nagao et al. / Journal of Organometallic Chemistry 669 (2003) 124ꢀ134
/
as that for 4 except that the evaporated reaction mixture
residue was crystallized from CH2Cl2ꢀhexane. Anal.
Calc. for C20H30Cl2Ir2FeSe2: C, 25.57; H, 3.22. Found:
3.10. Preparation of 13
/
Into a solution of 12 (47 mg, 0.046 mmol) in CH2Cl2
(5 cm3) was added PPh3 (12 mg, 0.046 mmol) and the
mixture was stirred for 1 day at r.t. The resultant
mixture was dried up in vacuo, and the residue was
washed with ether and then extracted with CH2Cl2.
Addition of hexane to the concentrated extract afforded
C, 25.55; H, 3.19%.
3.6. Preparation of 7
(1) Into a suspension of 6 (66 mg, 0.070 mmol) and 1a
(62 mg, 0.070 mmol) in THF (5 cm3) was added NaBPh4
(96 mg, 0.28 mmol) and the mixture was stirred at r.t.
for 6 h. The resultant mixture was dried up in vacuo and
the residue was extracted with CH2Cl2. Addition of
13×/CH2Cl2 as green crystals (39 mg, 66% yield). Anal.
Calc. for C39H47Cl4Ir2PPtSSe: C, 33.97; H, 3.43. Found:
1
C, 34.27; H, 3.56%. H-NMR (CDCl3, ppm): 2.07 (s,
Cp*), 5.29 (s, 2H, CH2Cl2), 7.16 (t, 6H, o-H of PPh3),
7.36 (t, 6H, m-H of PPh3), 7.48 (m, 3H, p-H of PPh3).
31P-NMR (CDCl3, ppm): ꢃ
ether to the concentrated extract gave 7×
/
CH2Cl2 as red
Calc. for
/
0.71 (s).
crystals (140 mg, 83%). Anal.
C89H102B2Cl2FeIr4Se4: C, 44.45; H, 4.28. Found: C,
44.53; H, 4.20%. 1H-NMR (CD2Cl2, ppm): 1.92 (s, 60H,
Cp*), 6.87 (t, 8H, p-H of BPh), 7.02 (t, 16H, m-H of
BPh), 7.29 (m, 16H, o-H of BPh). The presence of the
solvating CH2Cl2 was confirmed by recording 1H-NMR
spectrum in CDCl3. On the other hand, the single crystal
used for the X-ray diffraction study did not contain
CH2Cl2.
3.11. Preparation of 14
This complex was prepared from 3 (0.23 g, 0.27
mmol) and FeCl2 (35 mg, 0.28 mmol) by an analogous
method to that for 6. Black crystals (0.14 g, 58% yield).
Anal. Calc. for C20H30Cl2FeIr2SSe: C, 26.91; H, 3.39; S,
3.59. Found: C, 26.66; H, 3.29; S, 3.24%. FABMS m/z
857 ([14ꢃ
3.12. Preparation of 15
This cluster was obtained as 15×
/
Cl]ꢂ).
(2) Into a suspension of 6 (57 mg, 0.061 mmol) in
THF (5 cm3) was added NaBPh4 (83 mg, 0.24 mmol)
and the mixture was treated analogously. The yield of 7×
/
CH2Cl2 was 51 mg (70% based on Ir atom).
/CH2Cl2 from the
reaction of 3 (0.17 g, 0.20 mmol) and CoCl2 (40 mg, 0.30
mmol) carried out similarly to that for preparing 8.
Black crystals (79 mg, 39% yield). Anal. Calc. for
C44H66N2Cl6Co3Ir4S2Se2: C, 26.38; H, 3.32; N, 1.40.
Found: C, 26.18; H, 3.29; N, 1.50%.
3.7. Preparation of 8
A suspension containing 1a (0.18 g, 0.20 mmol) and
CoCl2 (39 mg, 0.30 mmol) in THF (7 cm3) was stirred at
r.t. for 1 day. The resultant mixture was filtered off and
the black solid remained was extracted with MeCN.
Addition of hexane to the concentrated extract afforded
black crystals of 8 (0.14 g, 68%). Anal. Calc. for
C44H66N2Cl6Co3Ir4Se4: C, 25.20; H, 3.17. Found: C,
25.25; H, 3.20%.
3.13. Preparation of 16
Into a suspension of 14 (0.10 g, 0.11 mmol) and 3
(0.094 g, 0.11 mmol) in THF (8 cm3) was added NaBPh4
(0.15 g, 0.44 mmol) and the mixture was stirred for 1
day. The resultant mixture was filtered off and the
remained solid was extracted with CH2Cl2. Addition of
hexane to the concentrated extract afforded the red
3.8. Preparation of 11
crystals of 16×
/
CH2Cl2 (0.13 g, 50% yield). Anal. Calc.
for C89H102B2Cl2FeIr4S2Se2: C, 46.25; H, 4.45. Found:
This cluster was prepared from 3 (0.17 g,0.20 mmol)
and [PdCl2(cod)] (57 mg, 0.20 mmol) as described for
preparing 4. Green crystals (0.13 g, 69% yield). Anal.
Calc. for C20H30Cl2Ir2PdSSe: C, 25.47; H, 3.21. Found:
C, 25.83; H, 3.31%. H-NMR (CDCl3, ppm): 2.12 (s,
Cp*).
1
C, 46.63; H, 4.61%. H-NMR (CD2Cl2, ppm): 2.24 (s,
60H, Cp*), 6.87 (t, 8H, p-H of BPh), 7.02 (t, 16H, m-H
of BPh), 7.31 (m, 16H, o-H of BPh). The presence of the
solvating CH2Cl2 was confirmed by recording 1H-NMR
spectrum in CDCl3.
1
3.9. Preparation of 12
3.14. X-ray diffraction studies
This cluster was obtained from 3 (0.17 g, 0.20 mmol)
and [PtCl2(cod)] (78 mg, 0.21 mmol) similarly. Green
crystals (0.12 g, 58% yield). Anal. Calc. for
C20H30Cl2Ir2PtSSe: C, 23.28; H, 2.93. Found: C,
23.06; H, 2.89%. 1H-NMR (CDCl3, ppm): 2.12 (s, Cp*).
The X-ray analyses of 5×
CH2Cl2, 14, and 15×CH2Cl2 were carried out at r.t. on a
Rigaku AFC7R diffractometer equipped with a gra-
phite-monocromatized MoꢀKa source. Intensity data
were corrected for the Lorentz-polarization effect and
/
1/2ClCH2CH2Cl, 6, 7, 8, 13×
/
/
/

Table 8
Crystallographic data for 5×
/
1/2ClCH2CH2Cl, 6, 7, 8, 13×
/
CH2Cl2, 14 and 15×CH2Cl2
/
5×1/2ClCH2CH2Cl
/
6
7
8
13×/CH2Cl2
14
15×/CH2Cl2
Formula
C21H32Cl3Ir2PtSe2
1128.29
Pbca (no. 61)
C20H30Cl2FeIr2Se2
939.57
C2/c (no. 15)
C90H103NB2FeIr4Se4 C44H66N2Cl6Co3Ir4Se4 C39H47Cl4Ir2PPtSSe C20H30Cl2FeIr2SeS C89H102B2Cl2CoIr4Se2S2
2314.16
Formula weight
Space group
Unit cell dimensions
2361.00
2097.26
C2/c (no. 15)
1379.14
P21/m (no. 11)
892.67
C2/c (no. 15)
¯
P1 (no. 2)
¯
P1 (no. 2)
˚
a (A)
20.265(5)
16.513(1)
16.375(2)
90.00
33.989(4)
8.919(2)
17.564(2)
90.00
11.391(5)
16.92(1)
23.61(1)
76.18(5)
77.54(5)
78.29(8)
4258(4)
2
29.125(4)
8.608(2)
23.951(1)
90.00
14.635(2)
12.635(1)
11.956(1)
90.00
33.725(5)
8.871(2)
17.505(3)
90.00
11.935(2)
16.937(2)
23.752(8)
75.98(2)
78.32(2)
77.99(1)
4304.5(2)
2
˚
b (A)
˚
c (A)
a (8)
b (8)
g (8)
90.00
90.00
109.96(1)
90.00
98.18(1)
90.00
93.013(8)
90.00
109.77(1)
90.00
3
˚
V (A )
Z
5479(1)
8
2.735
5004(1)
8
2.494
5943(1)
4
2.344
2207.8(4)
2
2.074
4928.1(1)
8
2.406
rcalc (g cmꢃ3
mcalc (cmꢃ1
Crystal size (mm3)
Number of data
)
1.841
81.64
1.785
73.65
)
177.47
143.39
125.11
103.53
131.68
0.50ꢄ
3610 (I ꢀ
262
/
0.20ꢄ
3.00s(I)) 3737 (I ꢀ
245
/0.10
0.40ꢄ
/
0.20ꢄ
3.00s(I)) 7240 (I ꢀ
919
/0.10
0.40ꢄ
/
0.20ꢄ
/
0.15
3.00s(I))
0.40ꢄ
3465 (I ꢀ
285
/0.20ꢄ
/
0.10
0.40ꢄ
4056 (I ꢀ
265
/0.30ꢄ
/
0.20
0.30ꢄ
4345 (I ꢀ
275
/
0.25ꢄ
3.00s(I)) 10815 (I ꢀ
1022
/0.20
0.40ꢄ
/
0.20ꢄ
/
0.20
3.00s(I))
/
/
/
/
3.00s(I))
/
3.00s(I))
/
/
Number of variables
Transmission factor
0.1345ꢀ/0.9991
0.2609ꢀ
/
0.9992
0.5026ꢀ/0.9968
0.0813ꢀ/0.9976
0.5935ꢀ/0.9995
0.6339ꢀ
/
0.9995
0.7569ꢀ0.9988
/
a
R
Rw or wR2
0.049
0.050
1.71
0.037
0.039
1.34
0.076
0.117
1.68
0.063
0.065
1.81
0.039
0.102
1.01
0.031
0.087
0.99
0.048
0.114
b
c
b
b
b
b
c
c
c
d
GOF
Residual peaks (eꢃ
1.09
1.58, ꢃ1.69
ꢃ3
˚
A
)
2.58, ꢃ
/
1.80
1.48, ꢃ
/
1.38
1.95, ꢃ
/
1.90
3.71, ꢃ
/
3.31
2.69, ꢃ
/
2.00
1.22, ꢃ
/
1.58
/
a
Rꢁ
/
SjjFojꢃ
Rwꢁ
[S w(jFojꢃ
wR2ꢁ
[S w(F2oꢃ
GOFꢁ
/
jFcjj/SjFoj.
b
c
/
/
jFcj)2/S wFo2]1/2 (wꢁ
/
[{s(Fo)}2ꢂ
/
(p2/4)F2o]ꢃ1).
/
/
F2c)2/S w(Fo2)2]1/2
.
d
/
[S w(jFojꢃ
/
jFcj)2/{(no. observed)ꢃ
/
(no. variables)}]1/2
.

134
S. Nagao et al. / Journal of Organometallic Chemistry 669 (2003) 124ꢀ134
/
Soc. 123 (2001) 3826;
for absorption (c-scans). Details of crystal and data
collection parameters are listed in Table 8.
(e) S. Kuwata, S. Kabashima, N. Sugiyama, Y. Ishii, M. Hidai,
Inorg. Chem. 40 (2001) 2034;
Structure solution and refinements were conducted by
using the TEXSAN program package [21]. The positions
of non-hydrogen atoms were determined by DIRDIF
PATTY [22] and were refined anisotropically. Hydrogen
atoms were placed at ideal positions and included at the
(f) F. Takagi, H. Seino, Y. Mizobe, M. Hidai, Organometallics 21
(2002) 694 (and references therein).
[2] (a) S. Nagao, H. Seino, Y. Mizobe, M. Hidai, Chem. Commun.
(2000) 207;
(b) S. Nagao, H. Seino, T. Okada, Y. Mizobe, M. Hidai, J. Chem.
Soc. Dalton Trans. (2000) 3546.
final stages of refinements with fixed parameters. For 5×
/
[3] H. Seino, Y. Mizobe, M. Hidai, Organometallics 19 (2000) 3631.
[4] H. Seino, Y. Mizobe, M. Hidai, New J. Chem. 24 (2000) 907.
[5] (a) D. Masui, T. Kochi, Z. Tang, Y. Ishii, Y. Mizobe, M. Hidai, J.
Organomet. Chem. 620 (2001) 69;
1/2ClCH2CH2Cl, half of the solvating dichloroethane
molecule is independent, in which the C(21) atom is
disordered over two positions with same occupancies.
Hydrogen atoms attached to C(21) were not included in
(b) T. Kochi, Y. Nomura, Z. Tang, Y. Ishii, Y.Mizobe, M. Hidai,
J. Chem. Soc. Dalton Trans. (1999) 2575;
the refinements. In 14 and 15×/CH2Cl2, the positions of
(c) Z. Tang, Y. Nomura, Y. Ishii, Y. Mizobe, M. Hidai,
Organometallics 16 (1997) 151;
bridging chalcogenido atoms were occupied by the Se
and S atoms with the same occupancies. These atoms
denoted as E in Figs. 6 and 7 as well as Tables 6 and 7
were refined, assuming the occupancies of 0.735 by only
Se.
(d) Z. Tang, Y. Nomura, S. Kuwata, Y. Ishi, Y. Mizobe, M.
Hidai, Inorg. Chem. 37 (1998) 4909;
(e) S. Kuwata, M. Andou, K. Hashizume, Y. Mizobe, M. Hidai,
Organometallics 17 (1998) 3429;
(f) K. Hashizume, Y. Mizobe, M. Hidai, Organometallics 15
(1996) 3303.
[6] Z. Tang, Y. Nomura, Y. Ishii, Y. Mizobe, M. Hidai, Inorg. Chim.
Acta 267 (1998) 73.
4. Supplementary material
[7] (a) P. Mathur, P. Payra, S. Ghose, Md.M. Hossain, C.V.V.
Satyanarayana, F.O. Chicote, P.K. Chadha, J. Organomet.
Chem. 606 (2000) 176;
Crystallographic data for the structural analysis have
been deposited with the Cambridge Crystallographic
(b) P. Mathur, S. Chatterjee, S. Ghose, M.F. Mahon, J.
Organomet. Chem. 587 (1999) 93 (and references therein).
[8] H. Seino, M. Hidai, Y. Mizobe, Chem. Lett. (2002) 920.
[9] D. Cauzzi, C. Graiff, C. Massera, G. Predieri, A. Tipicchio, D.
Acquotti, J. Chem. Soc. Dalton Trans. (1999) 3515.
Data Centre, CCDC nos. 201924ꢀ201930 for com-
/
pounds 6, 5, 7, 8, 14, 13, and 15, respectively. Copies
of this information may be obtained free of charge from
The Director, CCDC, 12 Union Road, Cambridge CB2
[10] J.A. Dean (Ed.), Lange’s Handbook of Chemistry, Tables 3ꢀ
McGraw Hill, New York, 1985.
[11] S. Schulz, M. Andruh, T. Pape, T. Heinze, H.W. Roesky, L.
/
10,
1EZ, UK (Fax: ꢂ44-1223-336033; e-mail: deposit@
/
ccdc.cam.ac.uk or www: http://www.ccdc.cam.ac.uk).
Haming, A. Kuhn, R. Herbst-Irmer, Organometallics 13 (1994)
¨
4004.
[12] J.S.L. Yeo, J.J. Vittal, W. Henderson, T.S.A. Hor, Inorg. Chem.
41 (2002) 1194.
Acknowledgements
[13] A. Bencini, M.D. Vaira, R. Morassi, P. Stoppioni, F. Mele,
Polyhedron 15 (1996) 2079.
Financial support by the JSPS FY 2001 ‘Research for
the Future Program’ and the Grant in Aid for Scientific
Research from the Ministry of Education, Science,
Sports, and Culture of Japan (No. 14078206) is appre-
ciated.
[14] R.E. Bachman, K.H. Whitmire, Inorg. Chem. 33 (1994) 2527.
[15] L.F. Dahl, P.W. Sutton, Inorg. Chem. 2 (1963) 1067.
[16] G. Gervasio, S.F.A. Kettle, F. Musso, R. Rossetti, P.L. Stan-
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[17] P. Braunstein, C. Graiff, C. Massera, G. Predieri, J. Rose´, A.
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[18] M. Iwasaki, Private communication (2001).
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[20] D. Drew, J.R. Doyle, Inorg. Synth. 28 (1990) 346.
[21] TEXSAN: Crystal Structure Analysis Package, Molecular Structure
Corp., The Woodlands, TX, 1985 and 1992.
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