Unexpected formation and conversion: Role of substituents of 1,3-ynones in the reactivity and product distribution during their reactions with Ru3(CO)12

Article abstract of DOI:10.1039/c8nj05573d

The reactions of Ru₃(CO)₁₂ with alkynyl ketones R₁CCC(O)R₂ (R₁ = Et, R₂ = Me (1); R₁ = Ph, R₂ = Me (2); R₁ = n-hexyl, R₂ = Ph (3); R₁ = H, R₂ = CH₃ (4); and R₁ = C(O)OCH₃, R₂ = OCH₃ (5)) proceeds in toluene with the formation of three ruthenoles (1a-3a), four CO-inserted binuclear clusters (1b-2b, 1c and 3c), a tetranuclear cluster 4a, a binuclear cluster 5a and a cyclotrimerization product 5b. Clusters 1a-3a, 1b, 2b, 1c and 3c were isolated from the reactions of Ru₃(CO)₁₂ with two equivalents of the corresponding ketones 1-3; 4a and 5a were collected by adding 4 and 5 to Ru₃(CO)₁₂ in molar ratios of 1:1 and 1:3, respectively; 5b was obtained by adding 5 to 5a in a molar ratio of 2:1. All compounds were characterized by NMR, FT-IR, and MS-ESI, and most of them were structurally verified by single crystal X-ray diffraction. Although the reaction products of 1-3 and Ru₃(CO)₁₂ exhibit similar cluster frameworks of usual ruthenoles and CO-inserted binuclear clusters, the isolation of the clusters 1b-2b, 1c and 3c reveals their strong dependence on both electronic and steric effects of the substituents of the 1,3-ynones 1-3. In addition, detailed investigations suggested that the high reactivity of the terminal hydrogen atom and electron-withdrawing property of the carbonyl group in 4 play a key role in the formation of 4a, and that the structurally unusual 5a is an intermediate in the formation of 5b.

Full text of DOI:10.1039/c8nj05573d

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Unexpected formation and conversion: role
of substituents of 1,3-ynones in the reactivity
and product distribution during their reactions
with Ru3(CO)12†
Cite this: New J. Chem., 2019,
43, 1478
Lei Xu,
Liping Jiang, Shasha Li, Guofang Zhang, * Weiqiang Zhang
and
Ziwei Gao
The reactions of Ru3(CO)12 with alkynyl ketones R1CRCC(O)R2 (R1 = Et, R2 = Me (1); R1 = Ph, R2 = Me (2);
R1 = n-hexyl, R2 = Ph (3); R1 = H, R2 = CH3 (4); and R1 = C(O)OCH3, R2 = OCH3 (5)) proceeds in toluene
with the formation of three ruthenoles (1a–3a), four CO-inserted binuclear clusters (1b–2b, 1c and 3c),
a tetranuclear cluster 4a, a binuclear cluster 5a and a cyclotrimerization product 5b. Clusters 1a–3a, 1b,
2b, 1c and 3c were isolated from the reactions of Ru3(CO)12 with two equivalents of the corresponding
ketones 1–3; 4a and 5a were collected by adding 4 and 5 to Ru3(CO)12 in molar ratios of 1 : 1 and 1 : 3,
respectively; 5b was obtained by adding 5 to 5a in a molar ratio of 2 : 1. All compounds were characterized
by NMR, FT-IR, and MS-ESI, and most of them were structurally verified by single crystal X-ray diffraction.
Although the reaction products of 1–3 and Ru3(CO)12 exhibit similar cluster frameworks of usual ruthenoles
and CO-inserted binuclear clusters, the isolation of the clusters 1b–2b, 1c and 3c reveals their strong depen-
dence on both electronic and steric effects of the substituents of the 1,3-ynones 1–3. In addition, detailed
investigations suggested that the high reactivity of the terminal hydrogen atom and electron-withdrawing
property of the carbonyl group in 4 play a key role in the formation of 4a, and that the structurally unusual
5a is an intermediate in the formation of 5b.
Received 2nd November 2018,
Accepted 6th December 2018
DOI: 10.1039/c8nj05573d
rsc.li/njc
To understand the mechanisms of their reactions, the reactions
of Ru3(CO)12 with NHCs, arenes, alkenes and alkynes were
Introduction
Ru3(CO)12 as a potent catalyst precursor attracted great interest extensively investigated.6 It was found that coordination atoms
of researchers in inorganic, organic and catalytic chemistry due usually play a very important role in the activation of neighbor-
to its high reactivity and unique catalytic activity.1 Ru3(CO)12 ing chemical bonds and construction of compound skeletons.7
has been widely used in the activation of chemical bonds2 and Meanwhile, it is well known that triruthenium clusters, ruthenoles,
in the construction of catalytic reactions.3 Besides, reactions of CO-inserted diruthenium clusters and tetrahedral tetraruthenium
transition metal clusters containing functionalized alkynes also clusters are the most common ruthenium cluster skeletons
attracted a lot of attention within the inorganic and organo- produced during the reactions of alkynes with Ru3(CO)12:8
metallic fields because of their potential applications in catalysis for example, P. J. Low and co-workers synthesized the tetra-
and as candidates in microelectronics and nanolithography.4 hedral tetraruthenium cluster Ru4(CO)12(m4-Z1:Z1:Z2:Z2-Me3SiCR
In recent years, carbonyl ruthenium clusters formed via the CC2CRCSiMe3) and ruthenole Ru2(CO)6{m-Z2-Z4-C(CRCSiMe3)Q
reaction of Ru3(CO)12 and alkyne derivatives were extensively inves- C(CRCSiMe3)C(CRCSiMe3)QC(CRCSiMe3)} by the reaction of
tigated, and some of them have been used in catalytic systems.5 Ru3(CO)12 with 1,6-bis(trimethylsilyl)hexa-1,3,5-triyne;9 P. Mathur
and co-workers isolated a triruthenium cluster [Ru3(CO)10
-
{m3-FcC2CRCFc}], a ruthenole [Ru2(CO)6{C4Fc2(CRCFc)2}2], CO-
inserted diruthenium clusters [Ru2(CO)6[m-Z1:Z1:Z2:Z2-{FcCR
CCC(Fc)–C(O)–C(Fc)CCRCFc}]] and [Ru2(CO)6[m-Z1:Z1:Z2:Z2-
{FcCRCCC(Fc)–C(O)–C(–CRCFc)C(Fc)}]] through the reaction of
FcCRCCRCFc (Fc = ferrocenyl) with Ru3(CO)12.10 In addition,
T. Takahashi and co-workers reported that an electron-withdrawing
group activates an alkyne and that an electron-donating group
deactivates an alkyne.11 In our recent studies, we have found that
Key Laboratory of Applied Surface and Colloid Chemistry, MOE/School of Chemistry
and Chemical Engineering, Shaanxi Normal University, Xi’an 710062, China.
E-mail: gfzhang@snnu.edu.cn
† Electronic supplementary information (ESI) available. Crystal structures of 1c
and 2a, CIF, checkcif, 1H NMR spectra, 13C{1H} NMR spectra, FT-IR spectra
and other electronic format. CCDC 1865423 (1a), 1865427 (1c), 1865428 (2a),
1865429 (2b), 1865430 (3c), 1865433 (4a), 1865431 (5a) and 1865432 (5b). For ESI
and crystallographic data in CIF or other electronic format see DOI: 10.1039/
c8nj05573d
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trirutheniums and ruthenoles are important intermediates in the similar to that of the usual triruthenium clusters, was found to
reactions of 1,3-ynones with Ru3(CO)12.12 We have also found that be an intermediate in the formation of the cyclotrimerization
electronic and steric effects of substituents in 1,3-ynones play very compound 5b.
important roles in the formation and conversion of ruthenoles:
(1) an electron-withdrawing group is beneficial to the formation
and conversion of ruthenoles; (2) an electron-donating group favors
the formation of ruthenoles, but disfavors the conversion of
Results and discussion
Syntheses and characterization
ruthenoles; and (3) a substituent with large steric hindrance prefers
only the formation of tail-to-tail coupling ruthenoles.12 Although
The thermal reactions of 1,3-ynones (1–5) with Ru3(CO)12 were
carried out in toluene at 90 1C in a nitrogen atmosphere. The
reactions of Ru3(CO)12 and different alkyne derivatives have been
reaction courses were monitored by the TLC technique. After
well explored, the studies usually focus on the reactions of
Ru3(CO)12 and alkynes with aromatic substituents.8–12 Herein, we
slow cooling, the solvents were removed and the residues were
chromatographed on silica gel with dichloromethane as the
choose 1,3-ynones containing alkyl groups or an acetyl group to
eluent.Scheme 1 illustrates the product distribution according
study the influence of the substituents on the product distribution
to the experimental results. The crystal and refinement data for
and their molecular structures during reactions of the 1,3-ynones
1a, 1c, 2a, 2b, 3c, 4a, 4b and 5a are listed in Table 1.
with Ru3(CO)12.
In this paper, we examined in detail the reaction process of
Ru3(CO)12 with 1,3-ynones R1CRCC(O)R2 (R1 = Et, R2 = Me (1);
The reaction of ynones (1–3) with Ru3(CO)12
R1 = Ph, R2 = Me (2); R1 = n-hexyl, R2 = Ph (3); R1 = H, R2 = CH3 (4); 1,3-Ynones 1–3 were each stirred in toluene at 90 1C in a
and R1 = C(O)OCH3, R2 = OCH3 (5)). The couplings and nitrogen atmosphere in a molar ratio of 2 : 1 with Ru3(CO)12
coordination of the 1,3-ynones with Ru3(CO)12 formed three for 1 h to yield three usual Ru(CO)3(Z4-ruthenole) derivatives
ruthenoles (1a–3a), four CO-inserted binuclear clusters (1b–2b, 1a–3a and two types of CO-inserted binuclear clusters 1b–2b
1c and 3c), a tetranuclear cluster 4a, a binuclear cluster inter- and 1c, 3c. The two expected clusters 2c and 3b were not
mediate 5a and a cyclotrimerization product 5b. Through a detected by the TLC, however. The structural characterizations
detailed examination of the reaction processes, we found that showed that each of the ruthenoles (1a–3a) contains a metalla-
the product distribution of the CO-inserted diruthenium clusters is cyclopentadienyl framework, similar in structure to the ruthenoles
dependent strongly on both electronic and steric effects of the we reported previously,12 in which two 1,3-ynone molecules are
substituents of the 1,3-ynones. Additionally, both the terminal coupled by the CRC units in the head-to-tail mode. Accordingly,
hydrogen atom and the carbonyl group in 3-butyn-2-one are very we choose 1a (Fig. 1) from 1a–3a as an example to describe the
important for the formation of 4a, and 5a, whose structure is not molecular structures of these clusters. The molecular structure of
Scheme 1 The product distribution of the reaction between Ru3(CO)12 and ynones (1–5). R1 = Et, R2 = Me (1); R1 = Ph, R2 = Me (2); and R1 = n-hexyl,
R2 = Ph (3).
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Table 1 Crystal and refinement data for 1a, 1c, 2a, 2b, 3c, 4a, 4b and 5a
Compounds
Formula
1a
1c
2a
2b
C18H16O8Ru2
562.45
0.71073
293(2)
C19H16O9Ru2
590.46
0.71073
C26H16O8Ru2
658.53
0.71073
153(2)
C27H16O9Ru2
686.54
0.71073
Fw (g molÀ1
Wavelength (Å)
T (K)
)
153(2)
153(2)
Crystal system
Space group
a (Å)
b (Å)
c (Å)
a (1)
b (1)
Triclinic
P1
9.536(3)
9.886(3)
10.826(3)
91.241(10)
94.723(10)
95.765(10)
1011.6(5)
2
Orthorhombic
Pna21
14.632(5)
15.540(4)
9.194(3)
90.00
90.00
90.00
2090.6(11)
4
1.876
Triclinic
P1
Monoclinic
P21/c
9.4633(13)
11.7500(15)
23.323(3)
90.00
99.820(5)
90.00
2555.4(6)
4
%
%
7.9800(14)
8.6097(16)
18.970(3)
86.303(5)
88.063(6)
74.729(5)
1254.5(4)
2
g (1)
V (Å3)
Z
Dc (Mg mÀ3
)
1.847
1.534
552
1.743
1.251
648
1.784
1.235
1352
Absorption coefficient (mmÀ1
F(000)
)
1.493
1160
Crystal sizes (mm)
Collected/unique
Rint
0.18 Â 0.15 Â 0.12
22 225/3916
0.0348
3916/0/254
1.185
0.16 Â 0.13 Â 0.12
22 236/4072
0.0348
4072/1/272
1.120
0.14 Â 0.13 Â 0.12
45 958/4922
0.0383
4922/0/328
1.050
0.17 Â 0.14 Â 0.12
27 930/5015
0.0519
5015/1/343
1.067
Data/restraints/parameters
GOF on F2
R1, wR2 [I Z 2s(I)]
R1, wR2 (all data)
0.0205, 0.0597
0.0216, 0.0606
0.585, À0.463
0.0233, 0.0567
0.0250, 0.0576
1.193, À0.620
0.0169, 0.0429
0.0179, 0.0437
0.554, À0.385
0.0294, 0.0691
0.0387, 0.0732
1.679, À0.579
Largest diff. peak/hole (e ÅÀ3
)
Compounds
Formula
3c
4a
5a
5b
C37H36O9Ru2
826.80
C16H3O13Ru4
807.46
C14H6O12Ru2
568.33
C36H36O24
852.65
Fw (g molÀ1
)
Wavelength (Å)
T (K)
0.71073
153(2)
0.71073
153(2)
0.71073
153(2)
0.71073
153(2)
Crystal system
Space group
a (Å)
b (Å)
c (Å)
a (1)
b (1)
g (1)
Triclinic
P1
8.457(2)
10.898(2)
19.590(5)
88.140(8)
83.336(8)
84.953(8)
1785.9(7)
2
Monoclinic
P21/n
13.736(4)
10.403(3)
15.643(5)
90.00
91.786(9)
90.00
2234.3(11)
4
Monoclinic
C2/c
13.385(5)
11.395(3)
11.933(4)
90.00
100.958(13)
90.00
1786.9(10)
4
Triclinic
P1
%
%
10.292(4)
11.043(4)
18.767(6)
76.244(12)
87.402(12)
74.255(12)
1993.6(12)
2
V (Å3)
Z
Dc (Mg mÀ3
)
1.537
0.898
836
2.400
2.716
1516
2.113
1.754
1096
1.420
0.122
888
Absorption coefficient (mmÀ1
F(000)
)
Crystal sizes (mm)
Collected/unique
Rint
0.16 Â 0.14 Â 0.13
64 541/7020
0.0416
0.16 Â 0.13 Â 0.11
77 373/4354
0.0408
0.14 Â 0.13 Â 0.10
9932/1758
0.0463
0.14 Â 0.12 Â 0.10
66 879/7815
0.0691
Data/restraints/parameters
7020/0/435
1.197
4354/0/298
1.147
1758/0/127
1.083
7815/0/553
1.097
GOF on F2
R1, wR2 [I Z 2s(I)]
R1, wR2 (all data)
0.0208, 0.0594
0.0231, 0.0608
0.544, À0.589
0.0168, 0.0411
0.0176, 0.0416
0.815, À0.678
0.0235, 0.0476
0.0303, 0.0500
0.374, À0.684
0.0462, 0.1024
0.0601, 0.1104
0.245, À0.288
Largest diff. peak/hole (e ÅÀ3
)
1a contains a metallacyclopentadienyl moiety, which is similar in the Ru1 atom and the alkyne molecule, and most of the Ru–C
structure to the carbonyl complexes [M(CO)(Z4-metallole)](M = Fe, bond lengths in the metallacyclopentadiene fall into two dis-
Ru, Os) formed by a combination of alkynes with group 8 tinct ranges, 2.2140(5)–2.3034(5) Å and 2.0655(4)–2.0843(5) Å.
metals.12,13 The FT-IR absorption bands in the range of In addition, the structure of 1a shows an eclipsed conformation
2014–2088 cmÀ1 were assigned to the terminal CO groups of 1a. of the carbonyls on the two ruthenium centers, with the dihedral
The 13C chemical shifts of the carbon atoms of the CRC bond angle of Ru1–Ru2–C15plane and Ru1–Ru2–C17plane being 3.612(6)1.
in 1a, located at 96.5 and 92.4 ppm in 1, moved downwards The special arrangement geometrically prevents an apical carbonyl
to 127.86 and 122.90 ppm, respectively, confirming a strong from being close enough to the ring metal Ru1 for a CO bridging
interaction between the CRC bonds and the three Ru atoms. conformation. Hence, all carbonyls are terminal with almost
The distance of the Ru–Ru bond is 2.7163(7) Å. The lengths of parallel Ru–C–O angles.
the C–C bonds (1.4010(3)–1.4668(3) Å) in the metallacyclo-
The crystal structures of the ruthenium carbonyl clusters
pentadiene (Ru2C3C4C9C10) reflect the interactions between 1b–2b, 1c and 3c exhibit a similar binuclear ruthenium
1480 | New J. Chem., 2019, 43, 1478--1486
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Fig. 3 ORTEP view of cluster 3c showing 50% ellipsoids. Selected bond
lengths (Å) and bond angles (1): Ru1–Ru2 = 2.7471(6); Ru1–C8 = 2.2104(4);
Ru1–C9 = 2.2836(4); Ru1–C24 = 2.0933(4); Ru2–C8 = 2.0715(4); Ru2–C23 =
2.2942(5); Ru2–C24 = 2.2546(4); C8–C9 = 1.4124(3); C23–C24 = 1.4054(3);
C23–C31 = 1.5027(3); C9–C31 = 1.4978(3); C22–C23 = 1.5217(3); C7–C8 =
1.5008(3); C22–O2 = 1.2129(3); C7–O1 = 1.2175(2); C31–O3 = 1.2097(3); and
C9–C31–C23 = 114.594(18).
Fig. 1 ORTEP view of cluster 1a showing 50% ellipsoids. Selected bond
lengths (Å) and bond angles (1): Ru1–Ru2 = 2.7163(7); Ru1–C3 = 2.2532(5);
Ru1–C4 = 2.2503(4); Ru1–C9 = 2.2140(5); Ru1–C10 = 2.3034(5); Ru2–C3 =
2.0843(4); Ru2–C10 = 2.0655(5); C3–C4 = 1.4010(3); C4–C9 = 1.4668(3);
C9–C10 = 1.4192(3); C2–C3 = 1.4923(3); C8–C9 = 1.5165(3); C2–O1 =
1.2066(3); C8–O2 = 1.1987(3); and C3–Ru2–C10 = 77.566(9).
displaying at 1681 cmÀ1. Each of the 1,3-ynone molecules
bonds to the ruthenium dimer via one p and one s inter-
actions, therefore providing each metal atom three electrons.
Apart from this, each metal also has three terminal carbonyl
groups, and the effective atomic number rule is obeyed for
the Ru–Ru bond.
On comparison of the structures of 1c and 3c with 1b–2b,
the crystal structures of 1c and 3c (taking 3c shown in Fig. 3 as
an example) each also show the usual staggered conformation
of the carbonyls, but two CRC units are joined through an
inserted carbonyl group in the head-to-tail coupling mode. The
structure of 3c consists of six terminal and one bridging
carbonyls. The distance of the Ru–Ru bond is 2.7471(6) Å.
framework to that reported by A. J. Blake and co-workers in the
reaction of Ru3(CO)9(m3-Z2:Z2:Z2-C16H16) and 1,2-diphenylethyne
earlier.14 The molecular structure of 2b, as an example, is depicted
in Fig. 2. The crystal structure of 2b exhibits a routine staggered
conformation of carbonyls, two CRC units being linked through
an inserted carbonyl group in the tail-to-tail coupling mode
(1b–2b). The distance of the Ru–Ru bond is 2.7383(3) Å, and the
dihedral angles between C7–C27–C17plane and C7–Ru1–C18plane
,
C8–Ru2–C17plane are 22.2271 and 39.0541, respectively. Two
phenylacetylene units are connected through a carbonyl group;
the FT-IR spectrum can demonstrate this point by a band
The dihedral angles between C9–C31–C23plane and C24–Ru1–C9plane
,
C8–Ru2–C23plane are 27.955(19)1 and 34.554(21)1, respectively.
The lengths of the Ru–C bonds fall mostly in the range
of 2.0715(4)–2.2942(5) Å, and the FT-IR absorption band at
1673 cmÀ1 confirms the existence of a bridging carbonyl group
between C23 and C9 atoms.
The reaction of 3-butyn-2-one (4) with Ru3(CO)12
Treatment of 3-butyn-2-one (4) with Ru3(CO)12 in a molar ratio of
1 : 1 in toluene at 90 1C for 1 h in a nitrogen atmosphere yielded a
single product [Ru4(CO)12{m4-Z1:Z2:Z1:Z2- (CH3C(O))CC}] (4a).
In addition, adding one equivalent of Ru3(CO)12 or 4 in 4a in
toluene at 90 1C did not give any new ruthenium clusters after 2 h
under stirring. The molecular structure of compound 4a has been
established by X-ray crystallography and depicted in Fig. 4. The
molecular structure of 4a consists of an octahedral arrangement
of four ruthenium atoms and two carbon atoms, with Ru–Ru
bond distances being in the range of 2.7235(5)–2.8068(8) Å. In
addition, the distance between C3 and C4 is 1.4771(4) Å, which is
elongated significantly, falling between the typical C–C single
bond and double bond.15 The alkyne ligand coordinates with
Ru1 and Ru4 in a Z1 mode, but with Ru2 and Ru3 in a Z2 mode.
The Ru–C bond distances in the octahedron fall in the range of
Fig. 2 ORTEP view of cluster 2b showing 50% ellipsoids. Selected bond
lengths (Å) and bond angles (1): Ru1–Ru2 = 2.7383(3); Ru1–C7 = 2.2713(2);
Ru1–C8 = 2.1759(3); Ru1–C18 = 2.0583(3); Ru2–C8 = 2.0896(2); Ru2–
C17 = 2.3084(2); Ru2–C18 = 2.1948(2); C7–C8 = 1.4166(1); C17–C18 =
1.4206(1); C7–C27 = 1.5188(2); C17–C27 = 1.5031(1); C27–O9 = 1.2063(1);
C18–C19 = 1.4980(1); C19–O1 = 1.2140(2); C8–C9 = 1.4991(2); C9–O1=
1.2166(1); and C7–C27–C17 = 114.762(8).
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Fig. 4 ORTEP view of cluster 4a showing 50% ellipsoids. Selected bond
lengths (Å) and bond angles (1): Ru1–Ru2 = 2.7734(5); Ru1–Ru3 = 2.7235(5);
Ru1–Ru4 = 2.8068(8); Ru2–Ru4 = 2.7359(5); Ru3–Ru4 = 2.7756(6);
Ru1–C3 = 2.1354(5); Ru2–C3 = 2.1752(6); Ru2–C4 = 2.1885(5); Ru3–C3 =
2.1863(5); Ru3–C4 = 2.1792(5); Ru4–C4 = 2.1249(6); C3–C4 = 1.4771(14);
C2–C3 = 1.5114(4); C2–O1 = 1.2090(3); Ru3–Ru3–C4 = 39.552(7)1; and
Ru1–C39–Ru2 = 89.885(7)1.
Fig. 5 ORTEP view of cluster 5a showing 50% ellipsoids. Selected bond
lengths (Å) and bond angles (1): Ru1–Ru1A = 2.8850(9); Ru1A–C3A =
2.1330(6); Ru1–C3 = 2.1330(6); C3–C3A = 1.3308(4); C2A–C3A = 1.4892(3);
C2A–O2A = 1.2064(4); C2A–O1A = 1.3481(3); C2–C3 = 1.4892(3); C2–O2 =
1.2064(4); and C2–O1 = 1.3481(3).
2.1752(6)–2.1885(5) Å, reflecting the interactions between the
Ru atoms and the alkyne ligands. The dihedral angles between
C3–C4–Ru4–Ru1plane and C3–Ru3–C4plane, C3–Ru2–C4plane are
70.8801 and 71.1171, respectively. M. I. Bruce and co-workers
synthesized the cluster Ru4(m4-PhC2CCPh)(CO)12, which is similar
in structure to 4a, by the reaction of more active Ru3(CO)10(MeCN)2
and PhC2C2Ph.16 Although the reactivity of Ru3(CO)12 is usually
lower than that of Ru3(CO)10(MeCN)2, the easy loss of the terminal
H atom of the C–C triple bond improves the reactivity of 4.
The reaction of dimethyl acetylenedicarboxylate (5) with
Ru3(CO)12
The reaction of Ru3(CO)12 with dimethyl acetylenedicarboxylate (5)
in a molar ratio of 1 : 3 in toluene at 90 1C for 30 min in a
nitrogen atmosphere afforded [Ru(CO)4{m2-Z1:Z1-(CH3OC(O))CC-
(C(O)OCH3)Ru(CO)4}] (5a) via the binding of the CRC bond
and the ruthenium dimer. The crystal structure of 5a (Fig. 5)
exhibits a binuclear ruthenium skeleton, with each Ru atom
binding with four terminal carbonyls and the Ru–Ru bond dis-
Fig. 6 ORTEP view of cluster 5b showing 50% ellipsoids. Selected bond
lengths (Å) and bond angles (1): C1–C2 = 1.3932(4); C2–C3 = 1.3952(3);
C3–C4 = 1.3998(5); C4–C5 = 1.3899(4); C5–C6 = 1.3935(3); C1–C7 =
tance being 2.8850(9) Å. The coordination of the alkynyl ketone (5) 1.5021(4); C2–C9 = 1.5048(5); C3–C11 = 1.4989(4); C4–C13 = 1.5088(4);
with Ru1 and Ru2 is in a Z1:Z1 mode. The distance of Ru1–C3 is
C5–C15 = 1.5023(5); C6–C17 = 1.5016(4); C7–O1 = 1.2024(3); C7–O2 =
1.3269(4); C9–O3 = 1.1951(3); C9–O4 = 1.3286(4); C11–O5 = 1.1979(3);
2.1330(6) Å, and the C3–C3A bond length is 1.3308(4) Å, which is
C11–O6 = 1.3249(7); C13–O7 = 1.1998(4); C13–O8 = 1.3248(4); C15–O9 =
between the typical C–C double bond and triple bond.15
1.2015(3); C15–O10 = 1.3280(4); C17–O11 = 1.2019(3); and C17–O12 =
When the reaction time of the above reaction was prolonged
from 0.5 h to 2 h, 5b, a cyclotrimerization product of 5, was
separated. The structure of 5b is illustrated in Fig. 6. The
1.3232(4).
isolation of 5b demonstrated that the reaction of Ru3(CO)12 reaction was performed at 90 1C for 30 min in a nitrogen
and 5 afforded a structurally similar cyclotrimerization compound atmosphere. The mixing of 5a with Ru3(CO)12 in toluene did
to those we reported previously.12
not give any new ruthenium clusters, however. By adding two
To clarify the formation process of the products at each step, equivalents of 5 in the cluster 5a in toluene at 90 1C, a
the reaction of Ru3(CO)12 with dimethyl acetylenedicarboxylate (5) cyclotrimerization product 5b was obtained. The formation of
was studied in detail and monitored by the TLC technique. It 5b by the reaction of 5a with 5 confirmed that 5a is a key
was observed that 5a was isolated as the main product when the intermediate in the generation of 5b.
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Transformation process from 1,3-ynones to products
reported previously, 5a is a binuclear ruthenium cluster.12
We speculate that the electron-withdrawing property of the carbonyl
group in 5 makes a great contribution to the formation of 5a and 5b.
Because 5 is a symmetric molecule with two electron-withdrawing
acetyl groups at the two sides of the CRC bond, they make the
electrons shift towards the carbonyl groups from the CRC
unit, thus helping coordination of the CRC bond with two
ruthenium atoms of the Ru3(CO)12 molecule in a Z1:Z1 mode,
and the CRC bond has therefore no ability to interact with
another ruthenium atom of the Ru3(CO)12 molecule to complete
the formation of a triruthenium cluster or to couple with another
alkynyl molecule to generate an usual stable ruthenole. In this
situation, an unstable metallacyclopentadienyl-containing inter-
mediate might be formed initially, and then the unstable inter-
mediate reacts quickly with another 5 molecule to produce 5b.
Therefore, 5a is an intermediate in the formation of 5b.
The reactions of Ru3(CO)12 and alkyne derivatives have been
well researched,8–12 and the electronic and steric effects of the
substituents of the alkynes were also investigated in detail by
T. Takahashi,11 and the results showed that substituents of the
alkynes direct, to some degree, the formation and conversion
of the intermediate products. We have also found a similar
tendency in the reactions of Ru3(CO)12 and 1,3-ynones.12 We
previously paid much attention to the reactions of Ru3(CO)12
with 1,3-ynones containing aromatic substituents, which are
usually electron withdrawing groups. For gaining insight into
the effects of electron donating groups on the product distribu-
tion and molecular structures of the isolated clusters during
the reactions of 1,3-ynones with Ru3(CO)12, the reactions of
Ru3(CO)12 with 1,3-ynones (1–3) were investigated in detail and
their reaction courses were traced by the TLC technique.
Experimental results showed that the reaction processes in
the formation of 1a–3a were similar to those we reported
earlier.12 However, it was found that different substituents in
the 1,3-ynones led to divergent product distribution in the
reaction processes. For example, the larger steric hindrance
of the substituents in 3 results in the formation of 3c as the
unique CO-inserted product in the reaction of 3 with Ru3(CO)12.
And, according to the explanations of T. Takahashi,11 the larger
steric hindrance and the electron-withdrawing property of the
phenyl ring in 2 exert 2b as the unique CO-inserted product in
the reaction of 2 with Ru3(CO)12.
4a is the unique product in the reaction of 3-butyn-2-one 4 with
Ru3(CO)12. However, the reaction of FPCRC–H (FP = (Z5-C5H5)-
Fe(CO)2) and Ru3(CO)12 afforded a triruthenium cluster Ru3(CO)9-
[m3-Z1:Z2:Z2-CRC-FP], which is different in structure from 4a.17
Concerning the structural difference between the two ruthenium
clusters whilst both precursors are terminal alkynes, we consider
that although the loss of the terminal hydrogen atom improves
the reactivity of CRC bonds in both alkynes, the weak influence
of the FP group in FPCRC–H induces it to strongly coordinate
with a ruthenium atom of Ru3(CO)12 in a Z1 mode, and then its
CRC bond interacts further with the other two ruthenium
atoms of the Ru3(CO)12 molecule in a Z2 mode to finish the
formation of the triruthenium carbonyl cluster. Meanwhile,
besides activating the CRC bond of 3-butyn-2-one by its terminal
hydrogen atom, the electron-withdrawing property of the carbonyl
group of 3-butyn-2-one promotes electron movement towards the
carbonyl side of the triple bond. Thus an unstable triruthenium
intermediate is probably generated by the coordination of the
triple bond with the Ru3(CO)12 molecule, and the CRC bond
interacts further with a ruthenium atom of another Ru3(CO)12
molecule or a Ru(CO)5 molecule produced by the decomposition
of Ru3(CO)12,18 in a Z2 mode to generate the tetranuclear ruthe-
nium carbonyl cluster 4a. Thus, both the high reactivity of the
Experimental
General procedures
All manipulations were carried out using standard Schlenk, and
the solvents were purified, dried and distilled in a nitrogen
atmosphere prior to use. Preparative TLC was performed on
20 Â 20 cm glass plates coated with silica gel (Merck GF254,
0.5 mm thick). FT-IR spectra were recorded on a Bruker Tensor 27
Fourier-transform spectrometer. 1H and 13C{1H} NMR spectra were
performed on a Bruker Avance 400 MHz spectrometer. ESI-mass
spectra were recorded on a Thermo Deca Max (LCMS) mass
spectrometer with an ion-trap mass detector, and high-resolution
mass spectra were recorded in the ESI mode on a Waters UPLC-Q-
TOF mass spectrometer. Elemental analyses were performed by
using a Vario EL III Elemental Analyzer. The structural measure-
ments of single crystals were carried out with a Bruker SMART
APEX-II CCD detector.
Synthesis
1,3-Diphenylprop-2-yn-1-one (1), 1-(2-chloro-phenyl)-3-phenylprop-2-
yn-1-one (2), 1-(4-nitro-phenyl)-3-phenylprop-2-yn-1-one (3),
1-(2-amino-phenyl)-3-phenylprop-2-yn-1-one (4) and 2-(3-phenyl-
propioloyl)phenylacetate (5) were used to react with Ru3(CO)12,
respectively. In order to get an optimum reaction condition for
the reactions of 1–5 with Ru3(CO)12, influences of the molar ratio
of Ru3(CO)12 to 1–5 (1: 1–1 : 5), reaction time (20 min–3 h) and
reaction temperature (60–110 1C) were investigated. The reaction
of 1 with Ru3(CO)12 was taken as an example. It was found that
the optimum molar ratio, reaction temperature and reaction time
are 1 : 2, 90 1C and 1 h, respectively. Their detailed synthetic
procedures are described as follows.
3-Hexyn-2-one (1) (0.0577 g, 0.6 mmol) and Ru3(CO)12
terminal hydrogen atom and the electron-withdrawing property of (0.1918 g, 0.3 mmol) were added to 15 mL toluene and heated
the carbonyl group in 3-butyn-2-one favor the formation of 4a. at 90 1C for 1 h, until the reaction solution changed from red to
The reaction of Ru3(CO)12 with acetylenedicarboxylate 5 afforded red-brown. The red-brown solution was cooled to room tem-
a binuclear cluster 5a and a cyclotrimerization product 5b. perature and the unreacted orange-red Ru3(CO)12 was precipi-
5b can be detected after adding 5 in the cluster 5a in toluene
at 90 1C. Unlike the structure of the triruthenium clusters we
tated and recovered (0.0493 g 0.0771 mmol). The residue was
chromatographed by a chromatographic column (457 mm
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length and 26 mm internal diameter) on silica gel with dichloro- 128.77 (Ph), 128.20 (Ph), 127.76 (Ph), 122.36 (Ph), 31.61 (CH3),
methane and petroleum ether, and the main products were eluted 28.25 (CH3). MS (m/z, ESI+), 661.892 (M+). Anal. calcd for
in the order of 1a, 1b and 1c, with the eluents being dichloro-
methane/petroleum ether (v/v) 1 : 10, 1 : 4 and 1 : 3, respectively.
And then the products were recrystallized by dichloromethane and
C
C
26H16O8Ru2: 661.894. Anal. found: C, 47.37; H, 2.56.
26H16O8Ru2 requires: C, 47.42; H, 2.45. M.p.: 143.2–144.8 1C.
[Ru(CO)3{l3-g1:g2:l3-g2:g1-(MeC(O))CC(Ph)C(O)C(Ph)C(MeC(O))-
hexane. The yields of the products were calculated based on the Ru(CO)3}] (2b). Yield: 29% (0.0597 g, 0.087 mmol). FT-IR
Ru3(CO)12 added at the beginning of a reaction.
(KBr, cmÀ1): 2921 vs, 2852 s, 2092 s, 2059 vs, 2018 vs, 1681 m.
[Ru(CO)3{l4-g1:g2:g1:g1(MeC(O))CC(Et)C(MeC(O))C(Et)Ru(CO)3}] 1H NMR (400 MHz, CDCl3) d 6.89–7.11 (m, 10H, C6H5), 1.90–1.96
(1a). Yield: 21% (0.0354 g, 0.063 mmol). FT-IR (KBr, cmÀ1): 2976 m, (d, 6H, CH3). 13C{1H} NMR (101 MHz, CDCl3) d = 195.03 (CO),
2937 m, 2879 m, 2088 vs, 2057 vs, 2014 vs, 1675 s. 1H NMR 194.23 (CO), 193.76 (CO), 169.14 (CRC), 163.94 (CRC), 131.08
(400 MHz, CDCl3) d 2.40–2.58 (m, 4H, CH2, CH3), 2.34–2.17 (Ph), 130.02 (Ph), 128.69 (Ph), 128.28 (Ph), 29.33. (CH3). MS
(m, 6H, CH3), 1.11–1.20 (m, 6H, CH3). 13C{1H} NMR (101 MHz, (m/z, ESI+), 689.887 (M+), 661.892 (M+ À CO). Anal. calcd for
CDCl3) d 205.02 (CO), 204.86 (CO), 201.78 (CO), 196.08 (CO), C27H16O9Ru2: 689.889. Anal. found: C, 47.10; H, 2.44. C27H16O9Ru2
195.39 (CO), 194.95 (CO), 194.82 (CO), 194.74 (CO), 194.43 (CO), requires: C, 47.23; H, 2.35. M.p.: 139.5 1C (dec.).
181.99 (CO), 127.86 (CRC), 122.90 (CRC), 36.33 (CH3), 33.06
[Ru(CO)3{l4-g1:g2:g1:g1-(PhC(O))CC(n-hexyl)C(PhC(O))C(n-
(CH3), 29.34 (CH2), 23.87 (CH2), 18.88 (CH3), 16.30 (CH3). MS hexyl)Ru(CO)3}] (3a). 1-Phenyl-3-hexyl-2-yn-1-one (3) (0.1286 g,
(m/z, ESI+), 565.893 (M+), 537.896 (M+ À CO), 509.901 (M+ À 2CO). 0.6 mmol) was used instead of 3-hexyn-2-one (1) to react with
Anal. calcd for C18H16O8Ru2: 565.894. Anal. found: C, 38.35; H, Ru3(CO)12 (0.1918 g, 0.3 mmol) and a similar synthetic procedure
3.01. C18H16O8Ru2 requires: C, 38.44; H, 2.87. M.p.: 139.3–140.5 1C. was employed. The isolated unreacted orange-red Ru3(CO)12 was
[Ru(CO)3{l2-g1:g2:l2-g2:g1-(MeC(O))CC(Et)C(O)C(Et)C(MeC- 0.0592 g (0.0926 mmol) and the main products 3a and 3c were
(O))Ru(CO)3}] (1b). Yield: 21% (0.0378 g, 0.064 mmol). FT-IR eluted using 1 : 5 and 1 : 4 (v/v) dichloromethane/petroleum ether
(KBr, cmÀ1): 2970 m, 2933 m, 2877 m, 2852 m, 2096 vs, 2034 vs, as eluents, respectively. Yield for 3a: 31% (0.0743 g, 0.093 mmol).
1967 vs, 1774 s, 1674 s. 1H NMR (400 MHz, CDCl3) d 2.02–2.64 FT-IR (KBr, cmÀ1): 3062 w, 2955 vs, 2924 vs, 2854 vs, 2087 s,
(m, 10H, CH2, CH3), 1.06–1.26 (m, 6H, CH3). 13C{1H} NMR 2060 vs, 2021 vs, 1981 s, 1671 s. 1H NMR (400 MHz, CDCl3)
(101 MHz, CDCl3) d 199.52 (CO), 196.70 (CO), 192.06 (CO), d 7.31–8.05 (m, 10H, C6H5), 2.10–2.56 (m, 4H, CH2), 1.08–1.26
173.52 (CO), 110.96 (CRC), 106.33 (CRC), 53.43 (CH3) 31.38 (m, 16H, CH2), 0.77–0.87 (m, 6H, CH3). 13C{1H} NMR (101 MHz,
(CH2), 30.38 (CH2), 20.35 (CH2), 17.34 (CH3), 16.16 (CH3). MS CDCl3) d 197.36, 194.69, 194.26 (CO), 171.47 (CRC), 168.00
(m/z, ESI+), 593.885 (M+), 537.892 (M+ À 2CO). Anal. calcd for (CRC), 134.95 (Ph), 133.96 (Ph), 133.08 (Ph), 132.33 (Ph),
C19H16O9Ru2 : 593.889. Anal. found: C, 38.53; H, 2.80. C19H16O9Ru2 129.96 (Ph), 128.33 (Ph), 123.60 (Ph), 121.81 (Ph), 33.06 (CH2),
requires: C, 38.65; H, 2.73. M.p.: 136.7 1C (dec.).
31.95 (CH2), 31.17 (CH2), 31.00 (CH2), 29.72 (CH2), 29.68 (CH2),
[Ru(CO)3{l2-g1:g2:l2-g2:g1-(MeC(O))CC(Et)C(O)C(MeC(O))- 22.43 (CH2), 22.25 (CH2), 13.98 (CH3), 13.89 (CH3). MS (m/z, ESI+),
C(Et)Ru(CO)3}] (1c). Yield: 23% (0.0407 g, 0.069 mmol). FT-IR 802.050 (M+). Anal. calcd for C36H36O8Ru2: 802.051. Anal. found: C,
(KBr, cmÀ1): 2969 m, 2922 m, 2850 m, 2100 vs, 2073 vs, 2026 53.97; H, 4.62. C36H36O8Ru2 requires: C, 54.13; H, 4.54. M.p.:
vs, 1676 s. 1H NMR (400 MHz, CDCl3) d 2.32–2.59 (m, 10H, 146.1–147.5 1C.
CH2, CH3), 1.24–1.28 (s, 6H, CH3). 13C{1H} NMR (101 MHz,
[Ru(CO)3{l2-g1:g2:l2-g2:g1-(PhC(O))CC(n-hexyl)C(O)C(PhC(O))C-
CDCl3) d 202.80 (CO), 201.93 (CO), 200.12 (CO), 196.62 (CO), (n-hexyl)Ru(CO)3}] (3c). Yield: 27% (0.0678 g, 0.082 mmol). FT-IR
191.93 (CO), 191.77 (CO), 176.49 (CO), 105.42 (CRC), 98.15 (KBr, cmÀ1): 3065 w, 2955 vs, 2927 vs, 2857 vs, 2086 vs, 2054 vs,
1
(CRC), 43.17 (CH3), 31.40 (CH3), 28.24 (CH2), 25.99 (CH2), 2023 vs, 1971 vs, 1673 m, 1649 m. H NMR (400 MHz, CDCl3)
20.37 (CH3), 15.20 (CH3). MS (m/z, ESI+), 593.886 (M+). Anal. d 7.45–8.15 (m, 10H, C6H5), 2.07–2.52 (m, 4H, CH2), 1.17–1.50
calcd for C19H16O9Ru2: 593.889. Anal. found: C, 38.51; H, 2.83. (m, 16H, CH2), 0.69–0.76 (m, 6H, CH3). 13C{1H} NMR (101 MHz,
C
19H16O9Ru2 requires: C, 38.65; H, 2.73. M.p.: 135.2 1C (dec.).
CDCl3) d 197.00 (CO), 196.29 (CO), 196.16 (CO), 195.04 (CO),
[Ru(CO)3{l4-g1:g2:g1:g1-(MeC(O))CC(Ph)C(MeC(O))C(Ph)- 194.83 (CO), 194.11 (CO), 179.57 (CRC), 169.45 (CRC), 135.15
Ru(CO)3}] (2a). 4-Phenyl-3-butyn-2-one (2) (0.0865 g, 0.6 mmol) was (Ph), 134.51 (Ph), 133.86 (Ph), 132.95 (Ph), 129.69 (Ph), 128.94
used instead of 3-hexyn-2-one (1) to react with Ru3(CO)12 (Ph), 128.36 (Ph), 126.55 (Ph), 34.06 (CH2), 32.24 (CH2), 31.02
(0.1918 g, 0.3 mmol) and a similar synthetic procedure (CH2), 30.56 (CH2), 29.71 (CH2), 29.23 (CH2), 28.65 (CH2), 27.80
was used. The isolated unreacted orange-red Ru3(CO)12 was (CH2), 22.19 (CH2), 21.96 (CH2), 13.87 (CH3), 13.74 (CH3). MS
0.0578 g (0.0904 mmol) and the main products 2a and 2b were (m/z, ESI+), 825.042 (M+), 797.051 (M+ À CO). Anal. calcd for
eluted using 1 : 6 and 1 : 5 (v/v) dichloromethane/petroleum C37H36O9Ru2: 825.046. Anal. found: C, 53.69; H, 2.53. C37H36O9Ru2
ether as eluents, respectively. Yield for 2a: 22% (0.0441 g, requires: C, 53.75; H, 4.39. M.p.: 141.5 1C (dec.).
0.067 mmol). FT-IR (KBr, cmÀ1): 2954 m, 2923 s, 2852 m,
[Ru4(CO)12{l4-g1:g2:g1:g2-(CH3C(O))CC}] (4a). 3-Butyn-2-one
2089 vs, 2058 vs, 2026 vs, 1995 vs, 1967 vs, 1708 m, 1676 m. (4) (0.0204 g, 0.3 mmol) was used instead of 3-hexyn-2-one (1) to
1H NMR (400 MHz, CDCl3) d 7.18–7.34 (m, 8H, C6H5), 6.96 react with Ru3(CO)12 (0.1918 g, 0.3 mmol) and the synthetic
(S, 2H, C6H5), 1.91 (S, 3H, CH3), 1.84 (S, 3H, CH3). 13C{1H} NMR process was similar. The isolated unreacted orange-red Ru3(CO)12
(101 MHz, CDCl3) d 204.23 (CO), 199.47 (CO), 195.39 (CO), was 0.0978 g (0.153 mmol) and the main product 4a was eluted
195.10 (CO), 194.19 (CO), 194.12 (CO), 177.81(CRC), 146.29 using 1 : 8 (v/v) dichloromethane/petroleum ether as eluent. Yield:
(CRC), 134.93 (Ph), 133.54 (Ph), 130.30 (Ph), 129.02 (Ph), 31% (0.0759 g, 0.094 mmol). FT-IR (KBr, cmÀ1): 3057 w, 2918 m,
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1
2852 w, 2080 vs, 2030 vs, 2003 vs, 1672 w. H NMR (400 MHz, and the transformation of the cluster skeletons suggested that
CDCl3) d 3.49 (s, 3H, CH3). 13C{1H} NMR (101 MHz, CDCl3) the diverse alkyl groups in the 1,3-ynones leads to the differ-
d 196.85 (CO), 190.45 (CO), 50.89 (CRC), 29.69 (CRC), 26.05 ence in their reactivities during their reactions with Ru3(CO)12.
(CH3). MS (m/z, ESI+), 809.579 (M+). Anal. calcd for C16H3O13Ru4: More importantly, we revealed that the product distribution of
809.577. Anal. found: C, 23.67; H, 0.51. C16H3O13Ru4 requires: C, the CO-inserted binuclear ruthenium clusters is dependent
23.80; H, 0.37. M.p.: 157.6 1C (dec.).
strongly on both the electronic and steric effects of the sub-
(5a). stituents of the acetylenic ketones, and considered that the
[Ru(CO)4{l-g2-(CH3OC(O))CC(C(O)OCH3)Ru(CO)4}]
Dimethyl acetylenedicarboxylate (5) (0.1279 g, 0.9 mmol) was high reactivity of the terminal H atom and the electron-
used instead of 3-hexyn-2-one (1) to react with Ru3(CO)12 withdrawing property of the carbonyl group in 3-butyn-2-one
(0.1918 g, 0.3 mmol) and the synthetic process was similar. are responsible for the formation of 4a. Besides, we found that
The isolated unreacted orange-red Ru3(CO)12 was 0.0846 g 5a is an intermediate in the formation of the cyclotrimerization
(0.1323 mmol) and the main products 5a and 5b were eluted product 5b, implying that cyclotrimerization of a 1,3-ynone
using 1 : 10 and 1 : 2 (v/v) dichloromethane/petroleum ether as undergoes probably a complicated transformation process or
eluents, respectively. Yield for 5a: 21% (0.0358 g, 0.063 mmol). one of two transformation processes, in which a triruthenium
FT-IR (KBr, cmÀ1): 3011 w, 2956 w, 2921 w, 2852 w, 2107 s, 2080 cluster, a biruthenium cluster and/or a ruthenole are formed
1
vs, 2053 vs, 2005 s, 1732 s, 1697 s. H NMR (400 MHz, CDCl3) as intermediates.
d 3.86 (s, 3H, CH3), 3.70 (s, 3H, CH3). 13C{1H} NMR (101 MHz,
CDCl3) d 192.51 (CO), 192.34 (CO), 191.74 (CO), 172.47 (CO),
Conflicts of interest
164.35 (CO), 117.50 (CRC), 53.56 (CH3), 52.58 (CH3). MS
(m/z, ESI+), 566.798 (M+), 528.797 (M+ À CO). Anal. calcd for
No conflicts of interest to declare.
C14H6O12Ru2: 566.796. Anal. found: C, 29.46; H, 1.15. C14H6O12Ru2
requires: C, 29.59; H, 1.06. M.p.: 137.3 1C (dec.).
Benzene-1,2,3,4,5,6-hexacarboxylic acid hexamethyl ester Acknowledgements
(5b). Yield: 64% (0.0822 g, 0.193 mmol). FT-IR (KBr, cmÀ1):
3013 w, 2958 m, 2918 w, 2851 w, 1736 vs. H NMR (400 MHz,
1
This work is supported by the National Natural Science Founda-
tion of China (21401124, 21171112).
CDCl3) d 3.88 (s, 18H, CH3). 13C{1H} NMR (101 MHz, CDCl3)
d 165.14 (CO), 133.90 (CRC), 53.48 (CH3). MS (m/z, ESI+),
426.083 (M+). Anal. calcd for C18H18O12: 426.080. Anal. found:
C, 50.63; H, 4.38. C18H18O12 requires: C, 50.71; H, 4.26. M.p.:
188.6–190.5 1C.
Notes and references
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Crystallography
The structural measurements were carried out with a Bruker D8
QUEST with a Photo 100 CMOS detector using a graphite
monochromated MoK radiation (l = 0.71073). The structure
was solved by direct methods (SHELXS-2014/97) and refined by
full-matrix least squares against F2 using SHELXL-2014 and
SHELXL-97 software.19 Non-hydrogen atoms were refined with
anisotropic thermal parameters. All hydrogen atoms were geo-
metrically fixed and refined using a riding model.
The single crystals of compounds 1a, 1c, 2a, 2b, 3c, 4a, 5a
and 5b suitable for single crystal X-ray diffraction were success-
fully grown from their dichloromethane/hexane solutions after
slow evaporation at 0 1C. Relevant crystallographic data are
given in Table 1. The crystallographic data for the structural
analysis have been deposited with the Cambridge Crystallo-
graphic Data Centre: 1865423 (1a), 1865427 (1c), 1865428 (2a),
1865429 (2b), 1865430 (3c), 1865433 (4a), 1865431 (5a) and
1865432 (5b).†
Conclusions
We isolated a series of new ruthenium clusters and a cyclo-
trimerization product by investigating the reactions of five
1,3-ynones with Ru3(CO)12. The activation of the 1,3-ynones
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