Ruthenium-tin complexes from the reaction of HSnPh3 with Ru3(CO)10(NCMe)2 and their reactions with bis(tri-t-butylphosphine)platinum

Article abstract of DOI:10.1016/j.jorganchem.2008.08.033

The compounds Ru₃(CO)₉(SnPh₃)₂(NCMe)(μ-H)₂ (1), Ru₃(CO)₁₀(SnPh₃)₂(μ-H)₂ (2), Ru(CO)₄(SnPh₃)₂ (3) and Ru(CO)₄(SnPh₃)(H) (4) were obtained from the reaction of Ru₃(CO)₁₀(NCMe)₂ with HSnPh₃ in hexane solvent. Compounds 1, 3 and the new compound Ru₃(CO)₇(SnPh₃)₃(NCMe)₂(μ-H)₃ (5) were obtained from reaction of Ru₃(CO)₁₀(NCMe)₂ with HSnPh₃ in a CH₂Cl₂ and MeCN solvent mixture. Compound 2 and the new compound Ru₃(CO)₉(SnPh₃)₃(μ-H)₃ (6) were obtained from reactions of 1 and 5 with CO, respectively. Compounds 2 and 6 eliminated benzene when heated to yield Ru₃(CO)₁₀(μ-SnPh₂)₂ (7) and Ru₃(CO)₉(μ-SnPh₂)₃ (8) which contain bridging SnPh₂ ligands. Compound 7 was found to react with Pt (PBu₃^t)₂ to yield the bis-Pt (PBu₃^t) adduct, Pt₂ Ru₃ (CO)₁₀ (PBu₃^t)₂ (μ₃ - SnPh₂)₂ (9) in 59% yield by the addition of Pt (PBu₃^t) groups to two of the Ru-Sn bonds to the bridging SnPh₂ ligands. Fenske-Hall molecular orbital calculations were performed to provide an understanding of the metal-metal bonding in the clusters of 7 and 9. Compounds 1, 2, 5, 6, 7 and 9 were characterized structurally by single crystal X-ray diffraction analysis.

Full text of DOI:10.1016/j.jorganchem.2008.08.033

Journal of Organometallic Chemistry 693 (2008) 3593–3602
Contents lists available at ScienceDirect
Journal of Organometallic Chemistry
journal homepage: www.elsevier.com/locate/jorganchem
Ruthenium–tin complexes from the reaction of HSnPh with Ru (CO) (NCMe)
3
3
10
2
and their reactions with bis(tri-t-butylphosphine)platinum
*
Richard D. Adams , Burjor Captain, Eszter Trufan
Department of Chemistry and Biochemistry, University of South Carolina, Columbia, SC 29208, United States
a r t i c l e i n f o
a b s t r a c t
Article history:
The compounds Ru (CO) (SnPh ) (NCMe)(
l
-H)2 (1), Ru (CO) (SnPh ) (
l
-H)2 (2), Ru(CO) (SnPh ) (3)
3
9
3
2
3
10
3 2
4
3 2
Received 15 August 2008
Accepted 18 August 2008
Available online 2 September 2008
and Ru(CO)
solvent. Compounds 1, 3 and the new compound Ru
reaction of Ru (CO)10(NCMe) with HSnPh in a CH
new compound Ru (CO) (SnPh -H) (6) were obtained from reactions of 1 and 5 with CO, respec-
tively. Compounds 2 and 6 eliminated benzene when heated to yield Ru (CO)10 -SnPh (7) and
Ru (CO) -SnPh (8) which contain bridging SnPh ligands. Compound 7 was found to react with
4
(SnPh
3
)(H) (4) were obtained from the reaction of Ru
(CO) (SnPh
Cl
3
(CO)10(NCMe)
2
with HSnPh
3
in hexane
3
7
3
)
3
(NCMe) -H) (5) were obtained from
2
(
l
3
3
2
3
2
2
and MeCN solvent mixture. Compound 2 and the
3
9
3
)
3
(
l
3
Keywords:
Ruthenium carbonyl
Tin
Platinum
Mixed metal clusters
Triphenylstannane
3
(
l
2 2
)
3
9
(
l
2
)
3
2
t
3
t
3
t
PtðPBu Þ to yield the bis-PtðPBu Þ adduct, Pt
2
Ru
3
ðCOÞ ðPBu Þ ðl3-SnPh
2
Þ
(9) in 59% yield by the addi-
2
10
3 2
2
t
3
tion of PtðPBu Þ groups to two of the Ru–Sn bonds to the bridging SnPh
2
ligands. Fenske–Hall molecular
orbital calculations were performed to provide an understanding of the metal–metal bonding in the clus-
ters of 7 and 9. Compounds 1, 2, 5, 6, 7 and 9 were characterized structurally by single crystal X-ray
diffraction analysis.
Ó 2008 Elsevier B.V. All rights reserved.
Ph
1
. Introduction
Ph
Sn
Sn
Ph
2
Sn
CO
Ru
It is well known that tin is an effective modifier of transition
Ru
Ru
Ru
Ru
metal catalysts [1]. Recently, it has been shown that polynuclear
metal carbonyl cluster complexes containing tin can serve as effec-
tive precursors to new families of multimetallic nanoscale catalysts
that exhibit high activity and selectivity for certain types of hydro-
genation reactions when they are deposited and activated on
mesoporous silica supports [2–5].
Ru
+
Ru
Ru
2
Ph Sn
CO
Sn
Sn
Ph
Ph
3
Ph SnH
H Ru (CO)
4
4
12
+
ð2Þ
+
3
We have shown that the tin-hydride compound HSnPh reacts
Ph
Sn
Ph
Sn
readily with polynuclear metal carbonyl cluster complexes to yield
a range of higher nuclearity metal cluster complexes having large
numbers of tin-containing ligands, Eq. (1)–(3) [3,6,7]. Bridging tin
ligands, SnPh [3,6–11], SnPh [3,7], and even naked Sn [10] are
2
commonly formed by the cleavage of 1–3 of the Ph groups from
the tin atom.
Ph
2
Sn
Ru
Ph
2
Sn
Ru
CO
SnPh
2
Ru
Ru
+
Ru
SnPh
Ru
Ph
2
Sn
Ru
Ru
2
Ph Sn
2
SnPh
2
Sn
Ph
Sn
Ph
Ph
Sn
Ph
Sn
2
Ph
Sn
2
Ru
Ru
SnPh
2
Ph
3
Sn
SnPh
3
1
27 °C
Ru
Ru
Ph
3
Sn
SnPh
3
Ru
Ru
Ru
Ru
ð1Þ
Rh Rh
Rh SnPh2 Ph
3
Sn
Rh
Rh
Ph
2
Sn
Rh (CO)
4 12
C
C
SnPh2
Ru
Ru
Rh
SnPh
2
+
4 Ph SnH
3
Ph
3
SnH Ph Sn
3
SnH
Ph Sn
2
2
Sn
Ph
2
Ph
Sn
Ph
ð3Þ
2 2
SnPh reacts with two equivalents of
We have shown that H
Ru(CO) to give the SnPh
*
Corresponding author.
E-mail address: Adams@mail.chem.sc.edu (R.D. Adams).
5
2
4
2
(l
2
bridged complex [Ru(CO) H] -SnPh )
0
022-328X/$ - see front matter Ó 2008 Elsevier B.V. All rights reserved.
doi:10.1016/j.jorganchem.2008.08.033

3
594
R.D. Adams et al. / Journal of Organometallic Chemistry 693 (2008) 3593–3602
that eliminates hydrogen when irradiated to give the complex Ru
CO) -SnPh ) with formation of a Ru–Ru bond, Eq. (4) [11]
2
-
2. Experimental
(
8
(
l
2
2.1. General data
Ph
Sn
2
Ph
Sn
2
+
Ph
2
SnH
2
ð4Þ
+hν
All the reactions were performed under a nitrogen atmosphere
2
Ru(CO)
5
Ru
Ru
Ru
Ru
H
by using the standard Schlenk techniques. Reagent grade solvents
were dried by the standard procedures and were freshly distilled
prior to use. Infrared spectra were recorded on an AVATAR 360
-
2 CO
H
t
3
We have also found that it is possible to add PdðPBu Þ and
t
3
1
31
PtðPBu Þ groups to transition metal–tin bonds by reactions with
FT-IR spectrophotometer. H NMR and P NMR were recorded
on a Varian Mercury 400 spectrometer operating at 399 and
t
3
t
the compounds PdðPBu Þ and PtðPBu Þ , e.g. Eq. (5) [12]. Ru
2
-
2
3
2
t
3
1
(
8 2 3
CO) (l-SnPh ) adds two Pt(PBu ) groups, the first one at the
1
62 MHz, respectively. P NMR spectra were externally referenced
Ru–Ru bond; the second one at one of the Ru–Sn bonds, Eq. (6) [11]
t
P Bu
Pt
3
SnPh
2
Ru
Ru
SnPh2
t
+
Pt(P Bu
3
)
2
Ru
Ru
Ph
2
Sn
ð5Þ
Ru
Sn
2
Ph Sn
Ru
Sn
t
3
Bu P Pt
t
PtP Bu
3
Ph
2
Ph
2
PBut
+
Pt(PBut
3 2
)
Ph2
Sn
3
+
Pt(PBut
3
)
2
Pt
Ru
Ru
Ru
Ph
Ph
Pt
SnPh2
Pt
Sn
o
t
t
ð6Þ
Ru
Ru
Bu P
Bu P
3
1
h, 25 C
3
Ru
+
CO
A number of years ago, Stone and coworkers reported that clus-
ter fragmentation occurred to yield the compounds Ru-
CO) (SnPh and Ru (CO) -SnPh (SnPh when Ru (CO)12
was allowed to react with Ph SnH [13]. Burgess et al. reported that
(CO)11(NCMe) with Ph SnH yielded the triruthe-
(CO)11(SnPh )( -H) formed by the displacement
against 85% ortho-H
3
PO
4
. Mass spectrometric measurements were
performed on a VG 70S instrument by using direct exposure probe
and electron impact ionization (EI). Triphenylstannane (HSnPh
and trimethylamine N-oxide Me O were purchased from
NO ꢀ 2H
Aldrich and were used without further purification. Ru (CO)12
and PtðPBu Þ were purchased from STREM and were used without
(
4
3
)
2
2
6
(
l
2
)
2
3
)
2
3
3
)
3
3
2
the reaction of Ru
nium complex Ru
3
3
3
t
3
3
3
l
2
of the labile MeCN ligand and the oxidative addition of the SnH
bond of the HSnPh to one of the ruthenium atoms [14]. Because
of our interests in ruthenium–tin compounds as catalyst precur-
sors, we have now investigated the reaction of HSnPh with Ru
CO)10(NCMe) [15] in hexane solvent and in a CH Cl /MeCN sol-
3 2
further purification. Ru (CO)10(NCMe) was prepared according to
3
the method described in the literature [15]. Product separations
were performed in air by TLC on glass plates by using Analtech sil-
ica gel 60 Å F254, 0.25 mm thickness.
3
3
-
(
2
2
2
vent mixture. In this work we have isolated and fully characterized
several new triruthenium compounds formed by multiple addi-
3 2 3
2.2. Reaction of Ru (CO)10(NCMe) with HSnPh in hexane
tions of HSnPh
ane solvent has yielded two new triruthenium complexes
Ru (CO) (SnPh (NCMe) -H) (1) and Ru (CO)10(SnPh -H)
2) by the addition of two equivalents of HSnPh to the
Ru (CO)10(NCMe) in addition to the known compounds
Ru(CO) (SnPh (3) [13] and Ru(CO) (SnPh )(H) (4) [16]. When
Ru (CO)10(NCMe) was allowed to react with HSnPh in the
CH Cl /MeCN solvent mixture yet another triruthenium complex
Ru (CO)
of three equivalents of HSnPh
3
to the triruthenium precursor. The reaction in hex-
A 29.1 mg (0.044 mmol) amount of Ru
pended in 20 mL hexane. A 110.5 mg (0.31 mmol) amount of
HSnPh in hexane was added to this suspension and stirred for
20 min at room temperature. The solvent was then removed in va-
cuo and the products were separated by TLC using 4:1 hexane–
methylene chloride solvent mixture to yield in order of elution:
3 2
(CO)10(NCMe) was sus-
3
7
3
)
3
2
(
l
3
3
3
)
2
(l
2
3
(
3
3
2
,
4
3
)
2
4
3
3
2
3
8.8 mg of colorless HRu(CO)
colorless Ru(CO) (SnPh (3) (7% yield) [13]; 11.8 mg of orange
-H) (2) (21% yield) and 7.4 mg of yellow
(NCMe)( -H) (1) (13% yield). Spectral data for
): 2106 (m), 2067 (w), 2051 (s), 2038
4 3
SnPh (4) (12% yield) [16]; 8.4 mg of
2
2
4
3 2
)
3
7
(SnPh
3
)
3
(NCMe)
2
(
l-H)
3
(5) was obtained by the addition
Ru
3
(CO)10(SnPh
(CO) (SnPh
CO (cm in CH
(s), 2023 (s), 2003 (s), 1982 (m). H NMR (CDCl
d = 7.27–7.67 (m, 30 H, Ph), 1.42 (s, 3H, Me), ꢁ13.89 (d, 1H, hy-
3
)
2
(
l
2
3
to the triruthenium cluster com-
Ru
3
9
3
)
2
l
2
ꢁ
1
plex. Surprisingly, the CO ligands were displaced in preference to
the MeCN ligands in the formation of 5. The MeCN ligands in 1
and 5 were replaced by treatment with CO to yield the fully car-
1: IR
m
2 2
Cl
1
3
, in ppm):
2
2
bonylated compounds 2 and Ru
pounds 2 and 6 eliminated benzene when heated to yield the
new compound Ru (CO)10 -SnPh (7) and the known compound
Ru (CO) -SnPh
3
(CO)
9
(SnPh
3
)
3
(l-H)
3
(6). Com-
dride,
J
H–H = 1.8 Hz), ꢁ15.04 (d, 1H, hydride,
JH–H = 2.1 Hz). Ele-
mental Anal. Calc.: C, 43.52; H, 2.72. Found: C, 44.33; H, 2.38%.
Spectral data for 2: IR mCO (cm in CH Cl ): 2118 (w), 2091 (m),
2 2
2043 (s), 2028 (s, sh), 2023 (s), 1985 (m). H NMR (d -benzene,
ꢁ
1
3
(l
2
)
2
1
6
3
9
(
l
2
)
3
(8) [12] which have bridging SnPh
2
ligands.
t
t
Compound 7 reacted with PtðPBu Þ to yield a bis-PtðPBu Þ adduct,
in ppm): d = 7.53–7.97 (m, 30 H, Ph), ꢁ15.03 (d, 1H, hydride,
3
2
3
t
3
t
3
2
2
2
Pt
2
Ru
3
ðCOÞ ðPBu Þ ð
l
-SnPh
2
Þ
(9) in which the PtðPBu Þ groups
J
H–H = 0.7 Hz,
J
119Sn–H = 27.3 Hz,
J
117Sn–H = 23.6 Hz), ꢁ16.68 (d,
1
0
2
3
2
1H, hydride, 2JH–H = 0.7 Hz,
2
J
119Sn–H = 37.5 Hz,
2
J
117Sn–H = 33.6 Hz).
bridge two of the Ru–Sn bonds. The syntheses and characteriza-
tions of these new compounds are described in this report.
Elemental Anal. Calc.: C, 42.9; H, 2.5. Found: C, 43.6; H, 2.5%.

R.D. Adams et al. / Journal of Organometallic Chemistry 693 (2008) 3593–3602
3595
2
.3. Reaction of Ru
3
(CO)10(NCMe)
2
with HSnPh
3
in CH
2
Cl
2
/MeCN
(CO)12
uct was separated by TLC by using 6:1 hexane–methylene chloride
solvent mixture to yield 6.8 mg of orange 7 (61%). Spectral data for
ꢁ
1
The reaction was done as follows: a 50 mg amount of Ru
0.078 mmol) was dissolved in 75 mL of CH Cl . To this solution
mL of MeCN was added and it was cooled to ꢁ78 °C in a dry
NO ꢀ 2H O in
.5 mL of MeCN was added drop-wise. The cooling bath was then
3
7: IR
m
CO (cm in CH
2
Cl
2
): 2100 (m), 2064 (w), 2048 (m), 2029 (s),
, in ppm): d = 7.00–7.71 (m, 20
1
(
2
2
1995 (m), 1864 (m). H NMR (CDCl
3
+
+
5
H, Ph). Mass Spec. EI/MS m/z: 1130, M ; 1073, M ꢁ2CO; 990,
+ + +
ice/acetone bath. Then a suspension of 23 mg of Me
3
2
M ꢁ5CO; 934, M ꢁ7CO; 848, M ꢁ10CO.
2
removed, and the solution was allowed to warm up to room tem-
perature. The reaction was considered complete when the solution
2.8. Thermal decomposition of 2 in an NMR tube
became yellow and the IR spectra showed the Ru
as major product. At this point, the reaction-mixture was filtered
over a silica gel column to remove the excess Me O. To
NO ꢀ 2H
this solution a 110.5 mg amount of HSnPh (0.315 mmol) was
3
(CO)10(NCMe)
2
A 11.4 mg amount of 2 (0.0089 mmol) was dissolved in d -tol-
8
uene and the solution was kept in an oil-bath at 80 °C for
1
3
2
10 min. H NMR of the 2 was taken at the beginning and another
1
3
H NMR was taken after the 10 min. The spectra revealed that
added. After 20 min at room temperature the reaction was stopped
and the solvent was removed in vacuo. The products were sepa-
rated by TLC by using 4:1 hexane–methylene chloride solvent mix-
the resonances corresponding to the hydrido ligands of 2 disap-
peared and new resonances corresponding to 7 and benzene
(7.13 ppm) formed.
ture to yield 6.8 mg of Ru
of 1 (19%) and 4.0 mg Ru
yield). Spectral data for 5: IR
3
(CO)12, 12.5 mg of 3 (6% yield), 19.1 mg
(CO) (SnPh (NCCH -H) (5) (3%
): 2086 (w),
, in ppm): d = 7.22–
3
7
3
)
3
3
)
2
(
l
3
3 9 2 3
2.9. Transformation of 6 to Ru (CO) (l-SnPh ) (8)
ꢁ
1
m
CO (cm
2 2
in CH Cl
2
7
1
1
1
027 (vs), 2008 (s), 1964 (m). 1H NMR (CDCl
3
A 7.4 mg amount of 6 (0.0046 mmol) was dissolved in 17 ml oc-
tane in a 100 mL three-neck flask. The solution was heated to re-
flux for 20 min. The reaction-mixture was cooled and the solvent
was removed in vacuo. After work up, 5.4 mg of 8 (85% yield)
was isolated. Compound 8 was reportedly obtained in a lower yield
.75 (m, 45H, Ph), 1.47 (s, 3H, Me), 1.43 (s, 3H, Me), ꢁ11.04 (s,
2
2
2
2
H, hydride,
H, hydride,
H, hydride,
J
119Sn–H = 45.1 Hz,
119Sn–H = 32.4 Hz,
J
J
117Sn–H = 40.5 Hz), ꢁ12.55 (s,
117Sn–H = 21.6 Hz), ꢁ13.02 (s,
J
2
2
J
119Sn–H = 42.6 Hz,
J117Sn–H = 13.5 Hz). Elemental
Anal. Calc.: C, 47.8; H, 3.33. Found: C, 48.1; H, 3.7%.
(20%) as product from the reaction of Ru
25 °C [12].
3 3
(CO)12 with HSnPh at
1
2
.4. Reaction of 5 with CO
t
3
2
.10. Reaction of 7 with PtðPBu Þ
2
A 12.8 mg amount of 5 (0.0078 mmol) was dissolved in 25 mL
benzene. This solution was purged with CO for 24 h at room tem-
perature. The solvent was then removed in vacuo and the products
separated by TLC by using 4:1 hexane–methylene chloride solvent
A 6.6 mg amount of 7 (0.0058 mmol) was dissolved in 13 mL
t
CH
2
Cl
2
.
To this solution
a
7.3 mg amount of PtðPBu Þ
3
2
(0.0122 mmol) was added and stirred at room temperature for
65 min. The color of the solution turned dark purple and IR spectra
showed the disappearance of the starting material. The solvent was
then removed in vacuo and the product was isolated by TLC by
mixture to yield 0.5 mg of yellow Ru
3 9 3 3 3
(CO) (SnPh ) (l-H) (6) (4%).
2.5. Reaction Ru (CO)12 with HSnPh under hydrogen
3 3
using 4:1 hexane–methylene chloride solvent mixture to yield
t
3
A 50 mg amount of Ru
0 ml of heptane in a 100 mL three-neck flask. The solution was
(0.271 mmol) and heated to hep-
was bubbled through it. After 90 min, the
reaction-mixture was cooled and the solvent was removed in va-
cuo. The products were separated by TLC by using 6:1 hexane–
methylene chloride solvent mixture to yield 55.2 mg (44%) of
3
(CO)12 (0.078 mmol) was dissolved in
6.6 mg of red Pt
2
Ru
3
ðCOÞ ðPBu Þ ðl3-SnPh
2
Þ
(9) (59%). Spectral
2
): 2079 (vw), 2031 (w), 2010
1
0
2
2
ꢁ1
5
data for 9: IR CO (cm in CH
m
2
Cl
1
added a 98 mg amount of HSnPh
tane reflux while H
3
3
(s), 1973 (w), 1844 (m), 1717 (w). H NMR (CDCl , in ppm):
d = 6.92–7.86 (m, 20 H, Ph), 1.21 (d, 18H, Me,
1
31
2
J
H–H = 13.1 Hz).
P
=
1
1
{ H} NMR (CDCl
3
, in ppm) at 25 °C: d = 109.77 (s, 2P,
J
Pt–P
+
+
+
5822.3 Hz). Mass Spec. ES/MS m/z: 1925, M +H ; 1848, M ꢁPh;
+
+
1770, M ꢁ2Ph; 1742, M ꢁ2PhꢁCO.
Ru
reaction are HRu(CO)
pound Ru (CO) -SnPh
of some yet uncharacterized compounds. Spectral data for 6: IR
3
- (CO)
9
(SnPh
3
)
3
(l
-H)
3
(6). Other compounds resulting from this
(4.9 mg; 3.7%) [15]; the known com-
2 3
) (8) (5.3 mg, 5% yield) [12], and traces
t
3
4
SnPh
3
2.11. Reaction of 1 with PtðPBu Þ
2
3
9
(
l
A 23.5 mg amount of 1 (0.0181 mmol) was dissolved in 20 mL
ꢁ1
1
t
3
m
(
CO (cm in hexane): 2083 (m), 2041 (s), 2028 (m, sh). H NMR
2
CH Cl
2
.
To this solution
a
21.6 mg amount of PtðPBu Þ
2
CDCl
3
, in ppm) at 25 °C: d = 7.22–7.7.59 (m, 45H, Ph), ꢁ14.60 (s,
(0.0361 mmol) was added. The solution was stirred at room tem-
perature for 3 h. The solvent was removed in vacuo and the prod-
ucts were then separated by TLC using 4:1 hexane–methylene
chloride solvent mixture to yield 2.0 mg of 9 (7%).
3
5
H, hydride). Elemental Anal. Calc.: C, 51.47; H, 3.29. Found: C,
1.07; H, 3.25%.
2.6. Reaction of 1 with CO
Crystallographic analyses. Orange single crystals of 1 suitable for
X-ray diffraction analysis were obtained by slow evaporation of
solvent from solutions in methylene chloride/hexane solvent mix-
tures at 5 °C. Orange single crystals of 2 and 7 suitable for X-ray
diffraction analysis were obtained by slow evaporation of solvent
from solutions in methylene chloride/hexane solvent mixtures at
room temperature. Yellow single crystals of 5 suitable for X-ray
diffraction analysis were obtained by slow evaporation of solvent
from solutions in methylene chloride/hexane solvent mixtures at
ꢁ25 °C. The crystals of 6 were grown from a methylene chloride/
hexane solvent mixture by cooling the solution to ꢁ25 °C. Dark
red single crystals of 9 suitable for X-ray diffraction analysis were
obtained by slow evaporation of solvent from a solution of methy-
A 10.0 mg amount of 1 (0.0077 mmol) was dissolved in 15 mL
hexane. The solution was then purged with CO for 2 h at room tem-
perature. The solvent was removed in vacuo and the product was
separated by TLC by using 4:1 hexane–methylene chloride solvent
mixture to yield 2.0 mg of orange 2 (20%).
2
.7. Transformation of 2 to Ru
3 2 2
(CO)10(l-SnPh ) (7)
A 12.6 mg amount of 2 (0.0098 mmol) was dissolved in 20 mL
benzene and was refluxed for 30 min. The orange color of the solu-
tion darkened and IR spectra revealed the appearance of a new
compound. The solvent was then removed in vacuo and the prod-

3
596
R.D. Adams et al. / Journal of Organometallic Chemistry 693 (2008) 3593–3602
lene chloride/pentane solvent mixtures at ꢁ25 °C. Each data crystal
was glued onto the end of a thin glass fiber. X-ray intensity data
were measured by using a Bruker SMART APEX CCD-based diffrac-
Compounds 1 and 7 crystallized in the triclinic crystal system.
The space group P1 was assumed and confirmed by the successful
ꢀ
refinement and solution of both structures. For compound 1 there
are two formula equivalents of the complex in the asymmetric
crystal unit. The asymmetric crystal unit of 7 contains only one for-
mula equivalent of the complex.
Compound 2 crystallized in the orthorhombic crystal system.
The space group Pbca was identified uniquely from the patterns
of systematic absences observed in the intensity data. There is only
one formula equivalent of the complex in the asymmetric crystal
unit. Compounds 5 and 9 crystallized in the monoclinic crystal sys-
tem. For 5 the systematic absences in the intensity data identified
tometer using Mo Ka radiation (k = 0.71073 Å). The raw data
frames were integrated with the SAINT+ program by using a nar-
row-frame integration algorithm [17]. Correction for Lorentz and
polarization effects were also applied with SAINT+. An empirical
absorption correction based on the multiple measurement of
equivalent reflections was applied in each analysis by using the
program SADABS. All structures were solved by a combination of di-
rect methods and difference Fourier syntheses, and refined by full-
2
matrix least-squares on F , using the SHELXTL software package [18].
All non-hydrogen atoms were refined with anisotropic thermal
parameters. Hydrogen atoms were placed in geometrically ideal-
ized positions and included as standard riding atoms during the
least-squares refinements. Crystal data, data collection parameters,
and results of the refinements are listed in Table 1.
1
the unique space group P2 /n. There is one formula equivalent of
the complex present in the asymmetric unit. One formula equiva-
lent of methylene chloride from the crystallization solvent also co-
crystallized with the complex. This molecule was included in the
analysis and was satisfactorily refined. For compound 9 the sys-
Table 1
Crystallographic data for compounds 1, 2, 5, 6, 7 and 9
Compound
1
2
5
Empirical formula
Formula weight
Crystal system
Lattice parameters
a (Å)
Ru
1298.35
Triclinic
3
Sn
2
NO
9
C
47
H
35
Ru
1286.31
Orthorhombic
3
Sn
2
O
10
C
46
H
33
3 3 2 7 65 2 2
Ru Sn N O C H Cl
54 .CH
1719.31
Monoclinic
13.5590(5)
19.4162(8)
20.5052(8)
112.602(1)
94.531(1)
99.354(1)
4857.7(3)
18.4513(5)
17.3186(4)
29.1451(7)
90.00
90.00
90.00
9313.3(4)
Pbca (#61)
8
1.835
2.063
294(2)
52.04
9175
558
1.029
0.009
0.0426, 0.0791
Multi-scan
1.000/0.774
0.829
10.1055(3)
b (Å)
c (Å)
44.4974(13)
14.7344(4)
90.00
97.233(1)
90.00
a
(°)
b (°)
(°)
c
3
V (Å )
6572.9(3)
ꢀ
Space group
Z value
P1 (#2)
P2
1
/n (#14)
4
4
q
l
calc. (g/cm3)
1.775
1.977
294(2)
53.60
23700
1135
1.002
0.008
0.0468, 0.0918
Multi-scan
1.000/0.613
1.289
1.737
1.927
150(2)
53.76
16384
762
1.122
0.032
0.0574, 0.1143
Multi-scan
1.000/0.751
1.353
ꢁ
(Mo K
a
) (mm 1
)
Temperature (K)
2H
max (°)
No. of observed reflections (I > 2
r
(I))
No. of parameters
Goodness-of-fit (GOF)a
Maximum shift in cycle
a
Residuals : R
1
; wR
2
Absorption correction
Maximum/minimum
Largest peak in final Difference map (e /Å )
ꢁ
3
6
7
9
3
Sn
3
O
9
C
63
H
47
Ru
1129.09
Triclinic
3
Sn
2
O
10
C
34
H
20
Pt
998.01
Monoclinic
2 3 2 2 10 58 5 12
Ru Sn P O C H H
74.0.5 C
Empirical formula
Formula weight
Crystal system
Lattice parameters
a (Å)
Ru
1607.29
Trigonal
25.0324(3)
25.0324(3)
17.0918(4)
90
90
120
8.8578(2)
19.8744(11)
16.7622(9)
21.9460(12)
90.00
90.971(1)
90.00
7310.0(7)
C2/c (#15)
4
1.814
5.180
294(2)
53.78
7196
370
1.058
0.007
0.0315, 0.0772
Multi-scan
1.000/0.589
1.811
b (Å)
c (Å)
13.7920(4)
16.2534(4)
105.965(1)
98.231(1)
92.430(1)
1882.38(8)
a
(°)
b (°)
(°)
c
3
V (Å )
9275.2(3)
ꢀ
ꢀ
Space group
Z value
P3 (#147)
P1 (#2)
6
2
q
l
calc (g/cm3)
1.727
1.960
294(2)
50.06
8086
593
1.031
0.001
0.0532; 0.1320
Multi-scan
1.00/0.86
1.298
1.992
2.536
294(2)
56.66
9328
442
1.016
0.001
0.0363, 0.0785
Multi-scan
1.000/0.832
1.097
ꢁ
(Mo K
a
) (mm 1
)
Temperature (K)
2H
max (°)
No. of observed reflections (I > 2
r
(I))
No. of parameters
Goodness-of-fit (GOF)a
Maximum shift in cycle
a
Residuals : R
1
; wR
2
Absorption correction
Maximum/minimum
Largest peak in final difference map (e /Å )
ꢁ
3
P
||)/P
hkl|Fobs|; R
¼ ½P
P
); GOF = [P
2(Fobs
a
2
2
obs
1=2, w = 1/
hklw(|Fobs| ꢁ |Fcalc|) /(ndata ꢁ nvari)]1/2
2
R = hkl(||Fobs| ꢁ |Fcalc
w
hklwðjFobsj ꢁ jFcalcjÞ = hklwF
ꢂ
r
.

R.D. Adams et al. / Journal of Organometallic Chemistry 693 (2008) 3593–3602
3597
tematic absences in the intensity data were consistent with space
groups Cc and C2/c. The latter was selected and confirmed by the
successful solution and refinement of the structure. The molecule
lies on a crystallographic twofold rotation axis. Also, one half for-
mula equivalent of pentane from the crystallization solvent was
cocrystallized with the complex. It was included in the analysis
and satisfactorily refined.
Compound 6 crystallized in the trigonal crystal system. There
were no systematic absences in the data. This is consistent with
ꢀ
either of the space groups P3 and P3. The latter was subsequently
confirmed by the successful solution and refinement of the struc-
tural analysis. There are three 1/3 molecules of 6 in the asymmetric
crystal unit. Each lies on a threefold rotation site. For the molecule
containing the atoms Ru(1) and Sn(1), all non-hydrogen atoms
were refined with anisotropic thermal parameters. The hydride li-
gand was located and refined with a fixed isotropic thermal param-
eter. Hydrogen atoms on the phenyl rings were placed in
geometrically idealized positions and included as standard riding
atoms during the least-squares refinements. For the molecule
which contains atoms Ru(1) and Sn(1), only the ruthenium, tin
and the carbonyl group atoms could be refined with anisotropic
thermal parameters. The carbon atoms on the phenyl rings are
slightly disordered and were constrained by using the SHELX FLAT
instruction and refined using isotropic thermal parameters. The
hydride ligand was located and refined with a fixed isotropic ther-
mal parameter. Hydrogen atoms on the phenyl rings were placed
in geometrically idealized positions and included as standard rid-
ing atoms during the least-squares refinements. The third molecule
was disordered over two orientations which were refined in the ra-
tio 60/40. The two orientations are mirror images of each other.
Fig. 1. An ORTEP diagram of the molecular structure of 1 showing 40% probability
thermal ellipsoids. Selected bond distances (in Å) and angles (°) are as follows: (for
molecule 1) Ru(1)–Ru(2) = 3.0844(6), Ru(1)–Ru(3) = 3.0797(7), Ru(2)–Ru(3) =
2.9144(6),
Ru(1)–Sn(1) = 2.6773(6),
Ru(2)–Sn(2) = 2.6488(6),
Ru(1)–N(1) =
2.099(5), Ru(1)–H(1) = 1.76(6), Ru(1)–H(2) = 1.90(6), Ru(2)–H(1) = 1.69(7), Ru(3)–
H(2) = 1.72(6): (for molecule 2) Ru(4)–Ru(5) = 3.0840(6), Ru(4)–Ru(6) = 3.0845(7),
Ru(5)–Ru(6) = 2.9118(7), Ru(4)–Sn(3) = 2.6799(6), Ru(5)–Sn(4) = 2.6553(6), Ru(4)–
N(2) = 2.116(5), Ru(4)–H(3) = 1.79(5), Ru(4)–H(4) = 1.69(5), Ru(5)–H(4) = 1.81(5),
Ru(6)–H(3) = 1.80(5).
The Ru
3
triangles in the two Ru
3
Sn
3
cores are offset by a rotation
cules in the crystal lattice of 1. Both molecules are structurally sim-
ilar. An ORTEP diagram of the molecular structure of one of these
two molecules is shown in Fig. 1. Compound 1 contains a triangu-
of 45.51° about their common C
ponents in the entire molecule were located from the difference
map and refined with fixed site-occupancy factors in the ratio
3
rotation axis. The disorder com-
lar cluster of three ruthenium atoms. There are two SnPh ligands
3
and the tin atoms lie essentially in the plane of the Ru trian-
3
6
0/40. Only the ruthenium and tin atoms were refined with aniso-
tropic thermal parameters. The hydride ligand was not located and
not included in the refinement. Hydrogen atoms on the phenyl
rings were placed in geometrically idealized positions and included
as standard riding atoms during the least-squares refinements.
gle. There are two bridging hydrido ligands, nine terminal CO
ligands and one MeCN ligand. The Ru–Sn bond distances,
Ru(1)–Sn(1) = 2.6773(6) Å,
Ru(2)–Sn(2) = 2.6488(6) Å
[Ru(4)–
Sn(3) = 2.6799(6) Å, Ru(5)–Sn(4) = 2.6553(6) Å], are slightly short-
er than those found in the mononuclear ruthenium–tin com-
pounds 3, 2.7058(3) Å and 2.7121(3) Å [5] and 4, 2.7108(3) Å
2.12. Molecular orbital calculations
[
16]. The Ru–Ru bond distances are significantly longer than those
All molecular orbital calculations reported herein were per-
found in Ru (CO)12, Ru–Ru = 2.854(1) Å [22]. The two longest
3
formed by using the Fenske–Hall (FH) method [19]. The calcula-
tions were performed by utilizing a graphical user interface
developed [20] to build inputs and view outputs from stand-alone
Fenske–Hall and MOPLOT2 binary executables [21]. Contracted
double-f basis sets were used for the Ru 4d, Pt 5d, Sn 5p, P 3p,
and C and O 2p atomic orbitals. The Fenske–Hall scheme is a non-
empirical approximate method that is capable of calculating
molecular orbitals for very large transition metal systems. For
these calculations, the input structures were obtained from the
positional parameters from the crystal structure analyses.
The molecular structures are not optimized by these calculations.
The t-butyl groups on the phosphine ligands and the phenyl groups
Ru–Ru bonds in 1, Ru(1)–Ru(2) = 3.0844(6) Å, Ru(1)–Ru(3) =
3.0797(7) Å, [Ru(4)–Ru(5) = 3.0840(6) Å, Ru(4)–Ru(6) = 3.0845(7)
Å], contain bridging hydrido ligands which are known to produce
bond lengthening effects [23]. The other bond is much shorter
Ru(2)–Ru(3) = 2.9144(6) Å [Ru(4)–Ru(5) = 2.9118(7) Å] and is only
slightly longer than those in Ru
located and refined crystallographically and bridge the Ru–Ru
bonds cis to the SnPh ligands, Ru(1)–H(1) = 1.76(6) Å, Ru(1)–
H(2) = 1.90(6) Å, Ru(2)–H(1) = 1.69(7) Å, Ru(3)–H(2) = 1.72(6) Å
[Ru(4)–H(3) = 1.79(5) Å, Ru(4)–H(4) = 1.69(5) Å, Ru(5)–H(4) =
3
(CO)12. The hydrido ligands were
3
1.81(5) Å, Ru(6)–H(3) = 1.80(5) Å]. The hydrido ligands are inequiv-
1
alent and the H NMR spectrum of 1 does exhibits two high-field
2
on the SnPh
2
ligands were replaced with hydrogen, e.g. PH
3
and
resonances at d = ꢁ13.89 (d, 1H,
J
H–H = 1.8 Hz), ꢁ15.04 (d, 1H,
2
SnH to simplify the calculations.
2
JH–H = 2.1 Hz) with appropriate H–H coupling, as expected. The
one MeCN ligand occupies an axial position on Ru(1) [Ru(4)]:
Ru(1)–N(1) = 2.099(5) Å, Ru(4)–N(2) = 2.116(5) Å. The one MeCN
3
. Results
ligand shows its methyl resonance at d = 1.42 (s, 3H) in the 1
H
Two new compounds Ru
3
(CO)
-H)
with HSnPh
3
9
(SnPh
(2) were obtained from the
in hexane solvent at
3
)
2
(NCMe)(
l
-H)
2
(1) (19%
NMR spectrum.
yield) and Ru
reaction of Ru
3
(CO)10(SnPh
3
)
2
(
l
2
Compound 2 is structurally similar to 1 except that the MeCN
ligand has been replaced by a terminally coordinated CO ligand
(see Fig. 2). The Ru–Ru and Ru–Sn bond distances in 1 are similar
to those in 1. The two bridging hydrido ligands are inequivalent
as in 1, and two high-field resonances were observed for these
3
(CO)10(NCMe)
2
room temperature. Both compounds were characterized by a com-
1
bination of IR, H NMR, mass spectra and by a single crystal X-ray
diffraction analyses. There are two symmetry independent mole-

3
598
R.D. Adams et al. / Journal of Organometallic Chemistry 693 (2008) 3593–3602
Fig. 2. An ORTEP diagram of the molecular structure of 2 showing 30% probability
thermal ellipsoids. The hydrogen atoms are omitted for clarity. Selected interatomic
bond distances (Å) and angles (°) are as follows: Ru(1)–Ru(2) = 3.0451(7), Ru(1)–
Ru(3) = 3.0812(8), Ru(2)–Ru(3) = 2.9042(8), Ru(1)–Sn(1) = 2.6891(7), Ru(2)- Sn(2) =
2
.6565(7), Ru(1)–H(1) = 1.74(7), Ru(1)–H(2) = 1.79(6), Ru(2)–H(1) = 1.75(7), Ru(3)–
H(2) = 1.77(6); Sn(1)–Ru(1)–Ru(3) = 97.67(2), Sn(2)–Ru(2)–Ru(1) = 105.24(2).
Fig. 3. An ORTEP diagram of the molecular structure of 5 showing 40% probability
thermal ellipsoids. Selected bond distances (in Å) and angles (°) are as follows:
Ru(1)–Ru(3) = 3.1284(6), Ru(1)–Ru(2) = 3.1312(6), (2)–Ru(3) = 3.1329(6), Ru(1)–
N(1) = 2.093(5), Ru(2)–N(2) = 2.112(7), Ru(1)–Sn(1) = 2.6610(6), Ru(2)–Sn(2) =
2.6681(6), Ru(3)–Sn(3) = 2.6745(6), Ru(1)–H(1h) = 1.63(7), Ru(1)–H(3h) = 1.86(9),
Ru(2)–H(1h) = 1.87(7), Ru(2)–H(2h) = 1.84(7), Ru(3)–H(2h) = 1.69(7), Ru(3)–
H(3h) = 1.61(9).
1
2
ligands in the H NMR spectrum, d = ꢁ15.03 (d, 1H, JH–H = 0.7 Hz),
2
ꢁ
16.68 (d, 1H, JH–H = 0.7 Hz).
Compound 1 was also obtained in 19% yield from the reaction of
Ru (CO)10(NCMe) with HSnPh in a CH Cl /MeCN solvent mixture
3 2 3 2 2
at room temperature. A small amount of 3 (6%) was also formed
but there was none of the compounds 2 and 4. Interestingly, how-
3 7 3 3 2 3
ever, a new compound Ru (CO) (SnPh ) (NCMe) (l-H) (5) was
obtained in a low yield (3%). Compound 5 was characterized by a
combination of IR, H NMR, elemental and a single crystal X-ray
Compounds 1 and 5 both react with CO (1 atm/25 °C) by substi-
tution of their MeCN ligands to yield the fully carbonylated com-
1
diffraction analyses. An ORTEP diagram of the molecular structure
of 5 is shown in Fig. 3. The molecule contains a triangular cluster of
three ruthenium atoms held together by three Ru–Ru bonds:
Ru(1)–Ru(3) = 3.1284(6) Å, Ru(1)–Ru(2) = 3.1312(6) Å, Ru(2)–
Ru(3) = 3.1329(6) Å. Each Ru–Ru bond also contains a bridging
hydrido ligand. Bridging hydrido ligands are known to produce
lengthening of the associated metal–metal bonds [23]. The hydrido
ligands were located and refined crystallographically. The hydrido
pounds
Ru (CO)
Ru
(SnPh
3
(CO)10(SnPh
3
)
2
(
l
-H)
2
(2)
(20%
yield)
and
3
9
3
)
3
(l
-H) (6), but the reaction of 5 with CO is slow
3
and the yield of 6 is very low (4%). Fortunately, we have found that
compound 6 can be prepared in a much better yield (44%) directly
from the reaction of Ru (CO)12 with HSnPh under a hydrogen
3 3
atmosphere in heptane solvent at reflux for 90 min. Compound 6
was characterized by single crystal X-ray diffraction analysis. OR-
TEP diagrams of the molecular structure of 6 is shown in Fig. 4.
In the solid state compound 6 crystallizes with three 1/3 molecules
in the asymmetric unit. Each one lies on a threefold rotation axis.
One of the molecules is disordered, see Section 2 above for details.
ligands lie in the plane of the Ru
Ru(1)–H(3h) = 1.86(9) Å, Ru(2)–H(1h) = 1.87(7) Å, Ru(2)–H(2h) =
.84(7) Å, Ru(3)–H(2h) = 1.69(7) Å, Ru(3)–H(3h) = 1.61(9) Å. All
3
triangle: Ru(1)–H(1h) = 1.63(7) Å,
1
three hydrido ligands are inequivalent and high-field resonances
with appropriate Sn–H couplings were observed for them in
Each molecule has crystallographic C
of the cluster has approximate C3h symmetry. The cluster consists
of a Ru triangle with three hydride-bridged Ru–Ru bonds. The Ru–
3 3 3
symmetry. The Ru Sn core
1
2
the H NMR spectrum at d = ꢁ11.04 (s, 1H,
J
119Sn–H = 45.1 Hz,
3
2
2
2
J
117Sn–H = 40.5 Hz), ꢁ12.55 (s, 1H,
J
119Sn–H = 32.4 Hz,
J
117Sn–H
=
Ru bond distances in 6 are similar in length to the hydride-bridged
2
2
*
2
1.6 Hz), ꢁ13.02 (s, 1H,
J
119Sn–H = 42.6 Hz,
J
117Sn–H = 13.5 Hz).
Ru–Ru bonds in 1, 2 and 5, Ru(1)–Ru(1 ) = 3.1298(10) Å, Ru(2)–
*
*
Each ruthenium atom contains one SnPh
3
ligand. All three SnPh
3
Ru(2 ) = 3.1062(10) Å, Ru(3A)–Ru(3A ) = 3.1351(16) Å. The Ru–Sn
ligands lie in the plane of the Ru triangle. Ignoring the phenyl
3
bond distances are also very similar to those found in 1, 2 and 5:
groups the other ligands the approximate symmetry is C3h. The
Ru(1)–Sn(1) = 2.6897(8),
Ru(2)–Sn(2) = 2.6892(7),
Ru(3A)–
Ru–Sn bond distances, Ru(1)–Sn(1) = 2.6610(6) Å, Ru(2)–Sn(2) =
Sn(3A) = 2.6833(13). Except for the disordered molecule, the hydr-
ido ligands were located and refined Ru(1)–H(1) = 1.68(6) Å,
Ru(2)–H(2) = 1.75(6) Å in the structural analysis. They are all
2
.6681(6) Å, Ru(3)–Sn(3) = 2.6745(6) Å, are similar to those ob-
served in 1 and 2. Compound 5 contains seven linear terminal
carbonyl ligands distributed as shown in Fig. 3 and two MeCN
ligands. The latter occupy axial coordination sites on Ru(1) and
1
equivalent and appear as a single resonance in the H NMR spec-
trum, d = ꢁ14.60. Compound 6 is structurally similar to the com-
Ru(2) cis to the SnPh
3
ligands on opposite sides of the Ru
3
plane:
3 9 3 3 3
pound Ru (CO) (GePh ) (l-H) that has been reported from the
Ru(1)–N(1) = 2.093(5) Å and Ru(2)–N(2) = 2.112(7) Å. The MeCN
ligands are inequivalent and two separate resonances are observed
for their methyl groups in the 1H NMR spectrum: d = 1.47 (s, 3H)
and 1.43 (s, 3H).
3 3
reaction of Ru (CO)12 with HGePh [24].
When compound 2 was heated to reflux in benzene solution for
30 min, it was converted to the new compound 7 in 61% yield. An
ORTEP diagram of the molecular structure of 7 is shown in Fig. 5.

R.D. Adams et al. / Journal of Organometallic Chemistry 693 (2008) 3593–3602
3599
Fig. 5. An ORTEP diagram of the molecular structure of 7 showing 30% probability
thermal ellipsoids. Selected interatomic bond distances (in Å) and angles (°) are as
follows: Ru(1)–Ru(2) = 2.9963(5), Ru(1)–Ru(3) = 2.9954(5), Ru(2)–Ru(3) = 2.8520(5),
Ru(1)–Sn(2) = 2.6377(5), Ru(1)–Sn(1) = 2.6593(5), Ru(2)–Sn(1) = 2.6547(5), Ru(3)–
Sn(2) = 2.6847(5); Sn(2)–Ru(1)–Sn(1) = 168.825(17), Ru(2)–Sn(1)–Ru(1) = 68.645(13),
Ru(1)–Sn(2)–Ru(3) = 68.489(13).
Fig. 4. An ORTEP diagram of the molecular structure of 6 showing 30% probability
thermal ellipsoids. The hydrogen atoms are omitted for clarity. Selected interatomic
bond distances (Å) and angles (°) are as follows: (molecule 1) Ru(1)–
Ru(1) = 3.1298(10), Ru(1)–Sn(1) = 2.6897(8), Ru(1)–H(1) = 1.68(6), (molecule 2)
Ru(2)–Ru(2) = 3.1062(10), Ru(2)–Sn(2) = 2.6892(7), Ru(2)–H(2) = 1.75(6), (molecule
Sn(2) = 2.6377(5) Å,
.6847(5) Å, are similar to the Ru–Sn bond distances found in 8.
Each ruthenium atom also contains three linear terminal carbonyl
ligands, two occupy axial sites perpendicular to the Ru triangle
and one lies in the plane of the Ru triangle. Compound 7 was
formed by the loss of two phenyl groups, one from each SnPh li-
Ru(2)–Sn(1) = 2.6547(5) Å,
Ru(3)–Sn(2) =
2
3
) Ru(3A)–Ru(3A) = 3.1351(16), Ru(3A)–Sn(3A) = 2.6833(13).
3
3
3
Compound 7 consists of a triangular cluster of three ruthenium
atoms with two SnPh ligands bridging adjacent Ru–Ru bonds.
gand, and the two hydrido ligands. These ligands combined to form
benzene which was confirmed by H NMR spectroscopy. Com-
1
2
The third Ru–Ru bond contains a bridging CO ligand. The tin
bridged Ru–Ru bond distances, Ru(1)–Ru(2) = 2.9963(5) Å, Ru(1)–
Ru(3) = 2.9954(5) Å, are similar to the Ru–Ru bond distances found
pound 7 is structurally similar to its germanium homolog, Ru
(CO)10 -GePh , which was obtained as a product of the thermal
decomposition of the compound Ru (CO) (GePh -H) [24].
3
-
(l
2 2
)
3
9
3
) (l
3
3
in the tris-SnPh
2
compound 8, [12] and are significantly longer
To obtain an understanding of the metal–metal bonding in 7, a
Fenske–Hall molecular orbital analysis was performed. The metal–
metal bonding in 7 is represented best by the contour diagrams of
than the CO bridged Ru–Ru bond, Ru(2)–Ru(3) = 2.8520(5) Å. The
Ru–Sn bond distances in 7, Ru(1)–Sn(1) = 2.6593(5) Å, Ru(1)–
Fig. 6. Contour diagrams for the molecular orbitals that show the metal–metal bonding in 7.

3
600
R.D. Adams et al. / Journal of Organometallic Chemistry 693 (2008) 3593–3602
t
3
except that it contains two additional PtðPBu Þ groupings that
were added as bridges across two of the Ru–Sn bonds as shown
2
in Fig. 7. The bridging SnPh ligands in 7 are converted into
triply bridging SnPh ligands in 9 upon the attachment of
2
t
the PtðPBu Þ groups. The Ru–Ru bonds in 9 are slightly shorter
3
than those in 7: Ru(1)–Ru(2) = 2.9622(6) Å and Ru(2)–Ru(2’) =
2
.8449(7) Å. The platinum-bridged Ru–Sn bond distance,
Ru(2)–Sn(1) = 2.7157(5) Å, has increased in length (approx.
.07 Å) compared to those in 7. The unbridged Ru–Sn bond
0
has also increased in length, but to a much smaller extent (ap-
prox. 0.02 Å), Ru(1)–Sn(1) = 2.6819(3) Å. Two of the terminal CO
ligands in 7 have shifted to bridging sites, one across each of
the new Pt–Ru bonds. A similar CO shift was observed when
t
3
PtðPBu Þ groups were added to the Ru–Sn bonds in the related
Fig. 7. ORTEP diagram of the molecular structure of 9 showing 30% probability
thermal ellipsoids. The hydrogen atoms are omitted for clarity. Selected interatomic
bond distances (in Å) each of the four independent molecules in the unit cell are as
t
3
compounds Pt
2
Ru
3
ðCOÞ ðPBu Þ ð
l
-SnPh
2
Þ , 10–12, n = 1–3 [12].
1
0
2
3
2
The Ru–Pt bond distance in 9, Ru(2)–Pt(1) = 2.7319(4), Å is very
similar to those in 10–12. However, the Pt–Sn distance, Pt(1)–
Sn(1) = 2.8328(4) Å, in 9 is slightly, but significantly longer, than
those in the compounds 10–12, range = 2.7433(7)–2.7922(15) Å
follows:
Ru(1)–Ru(2) = 2.9622(6),
Ru(1)–Sn(1) = 2.6819(3),
Ru(2)–Pt(1) = 2.7319(4),
Ru(2)–Sn(1) =
Ru(2)–Ru(2’) =
2
2
.7157(5), Pt(1)–Sn(1) = 2.8328(4),
.8449(7), Pt(1)–P(1) = 2.3035(12).
[
12]. Compound 9 was also obtained from the reaction of 1
t
six molecular orbitals shown in Fig. 6. The Ru–Ru bonding is repre-
sented by the HOMO at ꢁ6.94 eV and the HOMOꢁ8 at ꢁ10.58 eV.
The bonding between the ruthenium atoms and the bridging tin
atoms is best shown by the HOMOꢁ1, ꢁ8.67 eV, the HOMOꢁ2 at
with PtðPBu Þ but the yield was much lower, 7%. The low yield
3
2
may be due to the requirement to add a CO ligand which must
be scavenged from the reaction-mixture in order to form 9.
In previous studies it has been shown that the bonding of
t
3
ꢁ
9.23 eV, the HOMOꢁ12 at ꢁ12.26 eV and the HOMOꢁ13, at
13.01 eV, although the HOMOꢁ1 and HOMOꢁ12 also contain sig-
PtðPBu Þ groupings to homo- and heteronuclear metal–metal
ꢁ
bonds can be quite complex particularly when more than one
t
3
nificant contributions from the bridging CO ligand.
PtðPBu Þ grouping is involved [8,12,26]. To develop a better under-
When 6 was heated to reflux in octane solvent (125 °C), it was
converted into the known compound 8 in 85% yield by the elimina-
tion of three equivalents of benzene. Although 6 was not reported
previously, it seems likely that this compound is an intermediate in
standing of the metal–metal bonding in 9 and to compare it with
that in 7, a Fenske–Hall molecular orbital analysis was performed.
Contour diagrams of the molecular orbitals that show the interac-
tions of the two platinum atoms with the Ru Sn core of the cluster
3
2
the formation of 8 form the reaction of Ru
12].
In previous work it was shown that it is possible to add
3
(CO)12 with HSnPh
3
are shown in Fig. 8. The platinum atoms interact with the ruthe-
nium–tin bonds represented by the HOMOꢁ2 orbital in 7 to create
the HOMOꢁ2 orbital in 9. The platinum–ruthenium bonding is best
shown by the three orbitals: the symmetric HOMOꢁ2, ꢁ7.71 eV,
the antisymmetric HOMOꢁ12 ꢁ9.69 eV and the symmetric
HOMOꢁ13, ꢁ9.72 eV. The tin atoms are formally 5-coordinate,
but the platinum–tin interactions are weak and the only orbital
that exhibits any significant Pt–Sn interactions is the antisymmet-
ric HOMOꢁ22 at ꢁ11.51 eV. As in 7, the HOMO in 9 at ꢁ6.09 eV is
predominantly Ru–Ru bonding and the HOMOꢁ23 at ꢁ11.87 eV is
predominantly Ru–Sn bonding as it was in the HOMOꢁ13 in 7.
[
t
PtðPBu Þ groupings both to Ru–Sn bonds, Eqs. (5) [12] and (6)
3
[
11] and also to Ru–Ru bonds [25]. Accordingly, we also inves-
t
tigated the reaction of
Pt
7
with PtðPBu Þ . The compound
3
2
t
3
2
Ru
3
ðCOÞ ðPBu Þ ðl3-SnPh
1
0
2
2
Þ
(9) was obtained in 59% yield
2
t
from the reaction of 7 with PtðPBu Þ at room temperature in
3
2
6
5 min. An ORTEP diagram of the molecular structure of 9 is
shown in Fig. 7. In the solid state the molecule lies on a two-
fold rotation axis. The molecule is structurally similar to 7
Fig. 8. Contour diagrams of the FH molecular orbitals in 9 that show the metal–metal bonding.

R.D. Adams et al. / Journal of Organometallic Chemistry 693 (2008) 3593–3602
3601
Me
CC
N
Me
CC
N
+CO
SnPh3
H
SnPh3
H
Ru
Ru
Ru
+
HSnPh3
- NCMe
H
H
Ru(CO) (SnPh ) , 3
4 3 2
Ph Sn
3
Ru
Ru
Ph Sn
3
+
+
+
in hexane
Ru
Ru
Ru
Ru
HRu(CO) SnPh , 4
NC
C
4
3
Me
1
2
+
Pt(PBut3)2
2C H
+CO
NCMe
-
8
0 o
C
-2C H
6 6
-
6
6
Ph Sn
Ru
SnPh2
Ph Sn
Ru
SnPh2
Pt
2
2
+
Pt(PBut3)2
Pt
Ru
Ru
Ru
Ru
t
Bu P
PBut
3
3
7
9
Scheme 1.
Me
CC
N
Me
CC
SnPh3
N
SnPh3
Me
CC
Ru
SnPh
Ru
H
3
Ru
H
H
N
Ru
Ph Sn
H
3
H
+
HSnPh3
Ph Sn
+2CO
3
H
H
Ph Sn
3
+
Ru
Ru
Ru
Ru
Ru
Ru
in CH Cl /MeCN
H
-2 NCMe
2
2
Ru
Ru
NC
C
NC
C
SnPh
3
SnPh3
Me
Me
1
+
5
6
1
25 o
C
Ru(CO) (SnPh )
-3C H
4
3 2
6
6
3
Ru
Ph Sn
2
SnPh2
Ru
Ru
Sn
Ph
2
8
Scheme 2.
4
. Summary
lated compounds 2 and 6. In contrast to the fragmentation
products reported by Stone [13], we found that the triple HSnPh
addition product 6 was the principle product obtained from the
reaction of Ru (CO)12 with HSnPh when the reaction is per-
formed under hydrogen, although small amounts of the monoru-
thenium compound were also obtained. When heated,
compounds 2 and 6 eliminate benzene to form the planar cluster
compounds 7 and 8 that have two and three bridging SnPh li-
yielded a
Þ groups to two of
3
A summary of the reactions described in this report is shown
in Schemes 1 and 2. Three new triruthenium compounds: Ru
CO) (SnPh (NCMe)( -H) (1), Ru (CO)10(SnPh -H) (2) and
Ru (CO) (SnPh (NCMe) -H) (5) were obtained by ligand dis-
placements and multiple oxidative additions of HSnPh to Ru
CO)10(NCMe) . The reaction is slightly solvent dependent. The
reaction of HSnPh with Ru (CO)10(NCMe) in hexane produces
two oxidative additions of HSnPh to the Ru cluster to yield the
compounds 1 and 2, Scheme 1. Interestingly, one of the CO ligands
was displaced from the Ru (CO)10(NCMe) in preference to a
3
-
3
3
(
9
3
)
2
l
2
3
3
)
2
(l
2
3
7
3
)
3
2
(
l
3
3
3
3
-
(
2
2
t
gands, respectively. The reaction of 7 with PtðPBu
Þ
3
3
2
3 2
t
3
t
3
bis-PtðPBu
Þ adduct 9 by adding two PtðPBu
3
3
its Ru–Sn bonds. The Pt–Sn interactions are weak, but are still sig-
nificant as indicated by the molecular orbital calculations and the
Pt–Sn bond distances.
3
2
MeCN ligand to form 1. This is even more profound when the
reaction is performed in the presence of MeCN, Scheme 2. In this
case, both 1 and the tris-SnPh compound 5 were produced. Com-
3
pound 5 was formed by the displacement of two CO ligands in
preference to displacement of the MeCN ligands. The MeCN li-
gands in 1 and 5 can be displaced by CO to give the fully carbony-
As we have recently shown for related compounds, it is
anticipated that these new heterometallic complexes will also
serve as precursors to new nanoscale heterogeneous hydrogena-
tion catalysts when deposited and activated on suitable supports
[2–5].

3
602
R.D. Adams et al. / Journal of Organometallic Chemistry 693 (2008) 3593–3602
[
[
5] R.D. Adams, D.A. Blom, B. Captain, R. Raja, J.M. Thomas, E. Trufan, Langmuir 24
2008) 9223–9226.
6] R.D. Adams, B. Captain, W. Fu, M.D. Smith, Inorg. Chem. 41 (2002) 2302–2303.
Acknowledgements
(
This research was supported by the National Science Founda-
tion under Grant No. CHE-0743190. This report is dedicated to
the memory of Professor F. Albert Cotton.
[7] R.D. Adams, B. Captain, J.L. Smith Jr, M.B. Hall, C.E. Webster, Inorg. Chem. 43
(2004) 7576–7578.
[
8] R.D. Adams, B. Captain, R.H. Herber, M. Johansson, I. Nowik, J.L. Smith Jr, M.D.
Smith, Inorg. Chem. 44 (2005) 6346–6358.
[
9] R.D. Adams, B. Captain, L. Zhu, Organometallics 25 (2006) 2049–2054.
[
[
[
10] R.D. Adams, B. Captain, L. Zhu, Organometallics 25 (2006) 4183–4187.
11] R.D. Adams, E. Trufan, Organometallics, ASAP, 2008.
12] R.D. Adams, B. Captain, M.B. Hall, E. Trufan, X. Yang, J. Am. Chem. Soc. 129
(2007) 12328–12340.
13] J.D. Cotton, S.A.R. Knox, F.G.A. Stone, Chem. Commun. (1967) 965–966.
14] K. Burgess, C. Guerin, B.F.G. Johnson, J. Lewis, J. Organomet. Chem. 295 (1985)
C3–C6.
Appendix A. Supplementary material
CCDC 698764, 698763, 698765, 698766, 698767 and 698768
contains the supplementary crystallographic data for 1, 2, 5, 6, 7,
[
[
8
and 9. These data can be obtained free of charge from The Cam-
bridge Crystallographic Data Centre via www.ccdc.cam.ac.uk/da-
ta_request/cif. Supplementary data associated with this article
can be found, in the online version, at doi:10.1016/
j.jorganchem.2008.08.033.
[15] G.A. Foulds, B.F.G. Johnson, J. Lewis, J. Organomet. Chem. 296 (1985) 147–
53.
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556.
1
[
7
[17] SAINT+ Version 6.2a, Bruker Analytical X-Ray System, Inc., Madison, Wisconsin,
USA, 2001.
[
[
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