Ruthenium complexes containing hexamethylbenzene and butadienesulfonyl ligands: Synthesis and reactivity toward CO, nitrogen and phosphine ligands

Article abstract of DOI:10.1016/j.jorganchem.2015.05.023

The heterometallic tetranuclear complexes [(HMB)Ru(Cl)₂(5-η-CH₂CHCRCHSO₂)(Li)(THF)]₂ [R = H, 3; Me, 4] were synthesised by reaction of [(HMB)Ru(μ-Cl)Cl]₂ (1) (HMB = η⁶-C₆Me₆

Full text of DOI:10.1016/j.jorganchem.2015.05.023

Journal of Organometallic Chemistry 791 (2015) 107e118
Contents lists available at ScienceDirect
Journal of Organometallic Chemistry
journal homepage: www.elsevier.com/locate/jorganchem
Ruthenium complexes containing hexamethylbenzene and
butadienesulfonyl ligands: Synthesis and reactivity toward CO,
nitrogen and phosphine ligands
*
ꢀ
Jose Ignacio de la Cruz-Cruz, M. Angeles Paz-Sandoval
ꢀ
ꢀ
Departamento de Química, Centro de Investigacion y de Estudios Avanzados del IPN, Av. IPN # 2508, Col. San Pedro Zacatenco, Mexico D. F. 07360, Mexico
a r t i c l e i n f o
a b s t r a c t
Article history:
The heterometallic tetranuclear complexes [(HMB)Ru(Cl)2(5-
h
-CH2CHCRCHSO2)(Li)(THF)]2 [R ¼ H, 3; Me,
6-C6Me6) and an excess of
Received 2 March 2015
Received in revised form
7 May 2015
Accepted 8 May 2015
Available online 23 May 2015
4] were synthesised by reaction of [(HMB)Ru(
[CH2CHCRCHSO2Li] (R H, Me), whereas mononuclear complexes [(HMB)Ru(Cl)(1,2,5-
CH2CHCRCHSO2)] (R ¼ H, 7; Me, 8) were obtained when [CH2CHCRCHSO2K] was used. Complex [(HMB)
Ru(Cl)2(5-
-CH2CHCHCHSO2)(K)(THF)]2 (5) was spectroscopically detected by 1H and 13C NMR. Solution
experiments demonstrated that the above mentioned compounds transform into new ones by simply
dissolving or standing in solution. Isolation of the ion pair complex [(HMB)Ru(Cl)(5-
CH2CHCHCHSO2)(5- -CH2CHCHCHSO2K)] (9) and subsequent addition of AgBF4 results in the formation
of [(HMB)Ru(1,2,5- -CH2CHCHCHSO2)(5- -CH2CHCHCHSO2)] (10). Further reactivity of complexes 7 and
8 showed the addition reactions of a variety of ligands such as CO, deuterated and non-deuterated
pyridine and acetonitrile, resulting in complexes of the type [(HMB)Ru(Cl)(5- -CH2CHCRCHSO2)L]
[R ¼ H, L ¼ CO, 11; Py, 12, Py-d5, 12D; R ¼ Me, L ¼ Py, 13, Py-d5, 13D; R ¼ H, L ¼ CD3CN, 14D]. Treatment
with phosphines afforded the addition products [(HMB)Ru(Cl)(5-
m
-Cl)Cl]2 (1) (HMB ¼
h
¼
h-
h
h-
Keywords:
Ruthenium
Hexamethylbenzene
Butadienesulfonyl ligand
Butadienesulfinate salts
Deuterated nitrogen ligands
h
h
h
h
h
-CH2CHCHCHSO2)L] (L ¼ PMe3, 15;
PPh3, 16; PHPh2, 17) and the formation of the dichloride complexes [(HMB)Ru(Cl)2PR3] 15Cl, 16Cl and
17Cl, respectively, as by-products. Compounds 8 and 15 were characterized by single crystal X-ray
crystallography. Additionally, a comparative study with isoelectronic and related compounds was
undertaken.
© 2015 Elsevier B.V. All rights reserved.
1. Introduction
sandwich compounds [10]. Compounds based on Cp*MCl fragment,
such as (Cp*RuCl)4 and [Cp*M(
with lithium butadienesulfinate salts [CH2CHCRCHSO2Li] (R ¼ H,
2Li, Me 2LieMe) affording tetrameric [Cp*Ru(Cl)(1,2,5-
CH2CHCRCHSO2)(Li)]4 (A, Scheme 1) [11] and heterometallic tet-
ranuclear [Cp*M(Cl)2(5-
m
-Cl)Cl]2 (M ¼ Rh, Ir) react, in THF,
In the past few years, many “half-open sandwich” and “half-
sandwich” compounds have been prepared based on the well-
h
-
known
cyclic
cyclopentadienyl
(Cp)
or
pentam-
ethylcyclopentadienyl (Cp*) and the acyclic heteropentadienyl li-
gands [1,2]. The latter type of ligands incorporate heteroatoms such
as oxygen [3e5], nitrogen [6] and sulfur [7] into the pentadienyl
fragment. In spite of some achievements [8,9], the development of
the analogue chemistry to the above mentioned five-membered
h
-CH2CHCHCHSO2)(Li)(THF)]2 (M ¼ Rh,
3Cp*Rh [12]; Ir, 3Cp*Ir [13], Scheme 1) compounds. The tetrameric
A and 3Cp*Ir can be easily transformed into the mononuclear
[Cp*Ru(1-5-
h-CH2CHCRCHSO2)]
(B)
and
[Cp*Ir(Cl)(1,2,5-h-
CH2CHCHCHSO2)] (7Cp*Ir) by displacement of LiCl and THF,
Scheme 1, or using directly the potassium butadienesulfinate in
presence of Cp*MCln moieties. The size of the alkali-metal is crucial
in determining the nuclearity of the resulting complexes. The re-
actions with an excess of potassium butadienesulfinate afford labile
ligands, with the ancillary arene ligand HMB (HMB ¼
h
6-C6Me6)
remain poorly studied. The potential of this chemistry needs to be
evaluated because of the advantage offered by the coordination of
bioligands to the (h
6-arene)Ru fragment in comparison to Cp*Ru(II)
mononuclear ion pairs, such as [Cp*Ru(1,2,5-
h
-CH2CHCHCHSO2)(5-
h-CH2CHCHCHSO2K)] (9Cp*Ru) [11] and [Cp*Rh(Cl)(5-
h-
CH2CHCHCHSO2)(5-h-CH2CHCHCHSO2K)] (9Cp*Rh) [12]. The latter
reacts with AgBF4 to give the corresponding [Cp*Rh(1,2,5-h-
* Corresponding author.
E-mail address: mpaz@cinvestav.mx (M.A. Paz-Sandoval).
http://dx.doi.org/10.1016/j.jorganchem.2015.05.023
0022-328X/© 2015 Elsevier B.V. All rights reserved.

108
J.I. de la Cruz-Cruz, M.A. Paz-Sandoval / Journal of Organometallic Chemistry 791 (2015) 107e118
Scheme 1. Examples of half-open sandwich and half-sandwich compounds with butadienesulfonyl and butadienesulfinate ligands [11e14].
CH2CHCHCHSO2)(5-
h
-CH2CHCHCHSO2)] (10Cp*Rh) [12], Scheme 1.
butadienesulfonyl ligand.
The metathesis reaction with Cp*MCl2PR3 (M ¼ Rh, Ir, R ¼ Me,
Herein, we expand the chemistry of arene ruthenium com-
pounds bearing a butadienesulfonyl or butadienesulfinate ligands,
by describing a new series of compounds (HMB)Ru(Cl)L, (HMB)
Ru(Cl)2L0, (HMB)Ru(Cl)(L)(L0), (HMB)Ru(Cl)(L)(L00) and (HMB)Ru(L)2
(L ¼ butadiensulfonyl, L0 ¼ butadiensulfinate; L00 ¼ 2eꢀ donor). The
Ph) takes place in the presence of [CH2CHCHCHSO2K] (2K) to afford
[Cp*M(Cl)(5-
h
-CH2CHCHCHSO2)(PR3)] (M
¼
Rh, Ir,
R
¼
Me,
15Cp*M; R ¼ Ph, 16Cp*M, Scheme 1) [14] where the buta-
diensulfonyl ligand adopts both S (ZE) and W (EE) conformations,
the former being the kinetic product whereas the latter the ther-
modynamic. Addition of PMe3 and PPh3 to compound B (Scheme 1)
affords [Cp*Ru(1,2,5-
Ph) [15].
study also includes some derivatives with
p and s complementary
ligands, such as CO and phosphines; nitrogen ligands, such as
pyridine, acetonitrile and their corresponding deuterated species;
as well as ion-pair derivatives from the butadienesulfinate lithium
and potassium salts. Therefore, a detailed analysis of the steric and
electronic effects, as well as the influence of the substituents in
different ligands is described.
h
-CH2CHCRCHSO2)(PR03)] (R ¼ H, Me, R0 ¼ Me,
Related ruthenium sulfur chemistry of sandwich compounds
containing HMB and thiophene ligands, such as [(HMB)Ru(h5
-
C4R4S)][OTf]2 and [(HMB)Ru(
h
4-C4HR4S)][PF6] [R ¼ H, Me] have
shown unique and varied bonding modes, as well as ready acces-
sibility of the RuII/0 redox couple in (HMB)Ru(
[16]. The protonated reduced thiophene complex leads to CeS
h
4-C4R4S) [R ¼ H, Me]
2. Results and discussion
cleavage, affording the ring-opened thiapentadienyl complex
2.1. Synthesis and spectroscopic characterization of
(Hexamethylbenzene)Ruthenium(butadienesulfonyl) complexes
[(HMB)Ru(
Due to the known similarity in many aspects of the [(HMB)Ru(
Cl)Cl]2 chemistry to that of the neutral isoelectronic [Cp*M( -Cl)
h
5-C4H5S)][PF6] [17,18].
m-
m
2.1.1. Tetranuclear ruthenium-alkali-metal compounds 3e5 and
mononuclear ruthenium compounds 6e10
The chloro arene ruthenium dimer [(HMB)Ru(
reacted with an excess of lithium butadienesulfinate
Cl]2 (M ¼ Rh, Ir), as nicely and extensively shown by Bennett [19],
Maitlis [20] and co-workers, we decided to do a comparative study
between these precursors and their reactivity towards the
m-Cl)Cl]2 (1)

J.I. de la Cruz-Cruz, M.A. Paz-Sandoval / Journal of Organometallic Chemistry 791 (2015) 107e118
109
[CH2CHCRCHSO2Li] (R ¼ H, 2Li; Me, 2LieMe) in THF to give the
heterometallic complexes [(HMB)Ru(Cl)2(5- -CH2CHCRCHSO2)(-
Li)(THF)]2 [R ¼ H, 3, 53%; Me, 4, 40%], Scheme 2.
contrast to the molecular structure of 7, the methyl-substituted
compound 8 gave unquestionable evidence of the molecular
structure. The ruthenium atom is found in a distorted-octahedral
h
The K-analogue of complex 3, namely compound 5, was detec-
ted spectroscopically by 1H and 13C NMR in a tube-scale experi-
ment. It was prepared by mixing potassium butadienesulfinate-
based ligand 2K and 1. When 2K and 2KeMe are used in the re-
action with 1, instead of lithium salts 2Li and 2LieMe, mononuclear
yellow-orange 7 and yellow mustard 8 compounds are obtained in
54 and 46% yield, respectively, as described in Scheme 2. The for-
mation rate of 7 and 8 depends on the dielectric constant of the
solvent employed, being faster in chloroform (ε ¼ 4.7,1 h, 7; 30 min,
8) than in THF (ε ¼ 7.4, 3 h, 7; 2h, 8) or acetone (ε ¼ 20.7, 6 h, 7),
suggesting that the limiting step occurs via a neutral transition
state. In Scheme 3 a proposed mechanism for the formation of
compound 7 is described, where the addition of 2K to 1 afforded
the tetranuclear compound 5, spectroscopically observed, followed
by the elimination of THF which gave the saturated ion pair i. After
that, due to the loss of KCl, the ion pair i converts into the coor-
dinatively unsaturated intermediate ii with the immediate coor-
dination of the terminal double bond to afford 7. The same
mechanism is proposed for compound 8.
geometry and coordinated to one HMB ligand and one h1,2,5
-
butadienesulfonyl ligand through the terminal double bond and
sulfur atom; the chloride atom completes the electronic demand
for a coordinatively saturated complex 8, (Fig. 1).
Compound 8 crystallizes in a monoclinic system with a space
group C 2/c with four molecules in the asymmetric unit and THF as
solvate. The bond lengths C1eC2 and C3eC4 [1.405(8), 1.303(9) Å]
shown that the terminal double bond of the butadienesulfonyl
ligand was coordinated to the ruthenium center, which was clearly
demonstrated by the enlargement of the bond length due to the
retrodonation of C1eC2; while the internal C3eC4 double bond
distance is in agreement with the typical sp2 bond length. The
C4eS1, S1eO1 and S1eO2 bond lengths of 1.772(6), 1.459(5) and
1.472(4) Å reflect the typical values observed in 7Cp*Ir [13] and
tetranuclear complexes 3Cp*M [M ¼ Rh [12], Ir [13]] (Scheme 1).
The steric effect in the butadienesulfonyl ligand of 8 were re-
flected by the torsion angle [C1eC2eC3eC4 98.69(0.80)ꢁ], which is
similar than those of Cp*Ru(1,2,5-
[97.13(76)ꢁ] and wider compared with the carbonyl complex
Cp*Ru(1,2,5-
-CH2CHCHCHSO2)(CO) [88.52(27)ꢁ] [15a]. The lack of
h-CH2CHCHCHSO2)(PPh3)
The ion-pair complexes 6 and 9 (Scheme 2) were isolated from
the addition of 1.5 equiv of LiCl to 8 and the reaction of 7 with 2K in
a molar ratio 1:10 in 62.4% and 65.3%, respectively. In contrast,
when complex 8 was treated with 2KeMe under otherwise iden-
tical conditions as described for 9, an intractable mixture of (HMB)
Ru-containing complexes was obtained. Nonetheless, complex
h
planarity of the butadienesulfonyl ligand was reflected by the least-
squares planes [64.689 (0.579)ꢁ].
The IR spectra of 3 and 4 for the vibration modes of the SO2 in
the region of 1154e1016 cmꢀ1 showed strong and broad bands, due
to the coordination of the lithium atom, those for 4 (nas1154, 1124;
ns1021 cmꢀ1) were at higher wavenumber than those of 3 (nas1147,
1104; ns1016 cmꢀ1). The corresponding vibration modes of the SO2
group in the IR of the mononuclear compounds 7 (nas1187, 1111,
1080; ns1047 cmꢀ1) and 8 (nas1182, 1118, 1071; ns1043 cmꢀ1) show
narrow bands and, as expected, higher frequency values than those
of 3 and 4 (see Supporting information). The ion-pair complexes 6
[(HMB)Ru(Cl)(5-
(9Me) was detected by NMR spectroscopy. Addition of AgBF4 to 9 in
acetone solution resulted in the formation of [(HMB)Ru(1,2,5-
h-CH2CHCMeCHSO2)(5-h-CH2CHCMeCHSO2K)]
h
-
CH2CHCHCHSO2)(5-h-CH2CHCHCHSO2)] (10) in 53.4% yield,
Scheme 2.
Compound 7 crystallizes from CH2Cl2/hexane (1:2) solution
at ꢀ20 ꢁC, in the monoclinic space group P21/a, with four crystal-
lographically independent molecules in the asymmetric unit. The
quality of the crystals was poor and, unfortunately, no detailed
structural information could be obtained. Nevertheless, there was
no doubt about the composition and connectivity of the atoms in
this molecule, as described in the Supporting information. In
(
nas1143, 1122, 1074; ns1029 cmꢀ1
) and 9 (nas1156, 1110;
ns1039 cmꢀ1) also showed broad bands, due to the alkali-metal
interaction with the O]S]O fragment, as observed for com-
pounds 3 and 4. The IR was quite useful in order to identify indi-
rectly the presence or absence of the alkali-metal in the
butadienesulfinate and butadienesulfonyl complexes, as it has been
Scheme 2. Hexamethylbenzene ruthenium complexes with butadienesulfonyl and butadienesulfinate ligands.

110
J.I. de la Cruz-Cruz, M.A. Paz-Sandoval / Journal of Organometallic Chemistry 791 (2015) 107e118
Scheme 3. Proposed mechanism for the formation of compound 7.
established for different sorts of derivatives, some of them
described in Scheme 1. Compound 10 showed broader bands at nas
1179, 1112; ns1046 cmꢀ1, this was attributed to the presence of two
different butadienesulfonyl ligands coordinated to the ruthenium
atom.
The lability of compounds 3 and 4 hampered the detection of
the molecular ion in the mass spectra. However, compound 3
showed, through the (FAB)þtechnique, a peak detected at 989 m/z
assigned to [3-THF]þ, (see Supporting information). This data
supports the presence of a higher molecular weight than those
expected for discrete mononuclear entities. After several unsuc-
cessful attempts to get the molecular ion or the crystalline structure
of compound 3, complementary qualitative electrochemical and
physical Dynamic Laser-Light Scattering (DLS) techniques were
carried out, in order to support the nature of 3. The results obtained
from both techniques, support the higher aggregation state of 3
compare to the mononuclear compound 7, as described in detail in
the Supporting information. Further characterization of complexes
7e10 was accomplished by ESI þ TOF-MS. In the case of complex 6
it was possible to detect a peak at m/z ¼ 561, in the ESI-TOF-MS
mode, assigned to [(HMB)Ru(Cl)(5-h-CH2CHCMeCHSO2)(5-h-
CH2CHCMeCHSO2Li)] (9LieMe), without lithium, analogous to the
potassium derivative 9 (see Supporting information). This result
suggests the rearrangement of 6, under the ionization process
involved, to afford compound 1 along with 9LieMe, as described in
Scheme 4.
2.1.1.1. Solution reactivity and NMR spectroscopic characterization of
3e10. 1H and 13C NMR spectra obtained from THF-d8 solution
support the proposed structure for 3 and 4 in which the butadie-
nesulfonyl ligand shows typical chemical shifts for an non-
Fig. 1. Molecular structure of (HMB)Ru(Cl)(1,2,5-h-CH2CHCMeCHSO2) (8). Thermal
ellipsoids at 45% probability level. Selected bond distances (Å): C1eC2, 1.405(8);
C2eC3, 1.491(9); C3eC4, 1.303(9); C4eS1, 1.772(6); S1eO1, 1.459(5); S1eO2, 1.472(4);
Ru1eS1, 2.3144(15); Ru1eCl1, 2.4088(15). Selected bond angles (ꢁ): S1eRu1eCl1,
84.60(5); C1eC2eC3, 119.8(6); C2eC3eC4, 120.7(6); C3eC4eS1, 114.4(5). HMB(cent-
roid)-Ru,1.7839 Å.
coordinated unsaturated diene fragment (e.g.
d 5.18, H1; 5.15, H1';
8.00, H2; 5.89, H3 and 6.46, H4, for compound 3, which could be
compared with the chemical shifts of the precursor salt 2Li, 5.38,

J.I. de la Cruz-Cruz, M.A. Paz-Sandoval / Journal of Organometallic Chemistry 791 (2015) 107e118
111
spectrum as a sharp signal at 0.21 ppm (Dn ¼ 18.2 Hz), which
contrast to the broad signals observed in the heterometallic tetra-
nuclear complexes 3 (Dn ¼ 65.4 Hz) and 4 (Dn ¼ 79.5 Hz). It should
be mentioned that, in deuterated acetone, the 1H and 13C NMR
spectra of compound 6 do not have evidence of coordinated THF,
and it showed immediate transformation to produce starting ma-
terial 1 after losing 2LieMe, and also the regeneration of compound
8 after losing LiCl (see Supporting information).
The 1H and 13C NMR spectra showed that when 5 remained in
THF-d8 for 1h, a mixture of 5 and 7 in a 1:1 ratio is observed. After
3h there was a mixture of the potassium ion-pair 9 and 5, 7 in a
1.0:1.6:1.6 ratio, respectively; finally,
observed after 24 h (see Supporting information). Compound 9 has
only one set of signals for
1-butadienesulfonyl and the 1-buta-
a 1.0:2.7:2.0 ratio was
h
h
dienesulfinate ligands, which suggested that they were magneti-
cally equivalent, as observed in other ion-pair complexes [11,12].
The integration of 2:1 with respect to the HMB ligand in 9 confirms
the chemical similarity between both ligands (see Supporting
information). Compound 9 showed similar hydrogen and carbon
chemical shifts as those of 3e6, which supported the same h1 co-
ordination of the corresponding butadienesulfinate ligands (see
NMR data in the experimental section).
The bonding mode of the butadienesulfonyl ligand in 7 and 8 is
Scheme 4. Mass spectrometry fragments observed in the rearrangement of 6.
evident from NMR spectroscopy. The 1H NMR spectrum of 7 exhibit
*Observed by 1H and 13C{1H} NMR.
one signal of the HMB ligand at
butadienesulfonyl ligand that confirms the preferred h2 coordina-
tion mode of the terminal double bond (
¼ 3.61, H1; 3.73, H1';
5.04, H2) at lower frequencies, than those of the non-coordinated
internal double bond ( 5.86, H3; 6.40, H4), a similar spectrum
was detected for 8. This type of bonding was also confirmed in the
13C NMR spectrum for both complexes, where complex 8 exhibits
signals at higher frequencies corresponding to C3 and C4 non-
coordinated internal carbon atoms at 141.5, 149.2 ppm, respec-
tively, whereas the terminal-coordinated carbon atoms, C1 and C2,
resonate at 65.8, 93.4 ppm, respectively. 1H and 13C {1H} NMR
spectra of 10 were consistent with the different coordination
modes of both h1 and h1,2,5 butadienesulfonyl ligands to the
ruthenium atom.
d 2.12, and five hydrogens of the
H1; 5.31, H1'; 5.89, H2; 6.38, H3; 6.96, H4) [21a]. The highest fre-
quency signal, assigned to H2, suggested an interaction between H2
and one of the oxygen atoms from the SO2 moiety, this kind of
interaction is also observed in solution and in the solid state for
d
d
compound
[(HMB)Ru(Cl)(5-
h
-CH2CHCHCHSO2)(PMe3)]
(15)
[H2$$$O1, 2.3278 Å] (vide infra, Section 2.1.3) and in similar de-
rivatives previously reported [12]. An S conformation of the buta-
dienesulfonyl ligand in solution has been established for compound
3 by a t-ROESY experiment, which confirms the trans and cis
coupling of the S conformer, showing spatial interaction between
hydrogens H4 and H3, H3 and H1, and H2 and H10, (see Supporting
information). A singlet at
and two pairs of signals at
d
d
1.96 is assigned to the coordinated HMB,
1.75, 3.59 as multiplets and 1.71, 3.56 as
singlets are assigned to coordinated THF and the solvent residual
signal, respectively. The corresponding carbon resonances of 3 for
2.1.2. Reactivity of compounds 7 and 8 with CO and nitrogen donor
ligands
C1, C2, C3 and C4 at
d 119.8, 133.5, 128.6 and 138.2 confirm that the
The synthesis of Ru(II) compounds of general formula [(HMB)
diene fragment is not coordinated.
Ru(Cl)(5-
h
-CH2CHCRCHSO2)L] [R ¼ H, L ¼ CO, 11; Py, 12, Py-d5, 12D;
According to the almost identical chemical shifts and coupling
constants of compounds 3 and 4 we proposed similar molecular
structures in solution. Moreover, the 7Li NMR spectra of 3 and 4
showed broad singlets at 0.18 and 0.17 ppm. The analogy between
the NMR spectroscopy data of 5 with 3 and 4 (except H3 and C3 in
4) is indicative that the alkali-metal (M ¼ Li, K) is interacting
exclusively with the sulfonyl group, where a charge is delocalized
along the OeSeO atoms, as it has been reported for other buta-
dienesulfinate derivatives [21a,22].
Based on the similar chemical, spectroscopic and structural
behavior of 3 and 4 with 3Cp*M (M ¼ Rh [12], Ir [13]) (Scheme 1),
and the qualitative results obtained by electrochemical and DLS
experiments, we propose analogue molecular structures for 3 and 4
to those confirmed for the Cp* derivatives, where the lithium
butadienesulfinate ligand is solely added to the corresponding
precursors.
R ¼ Me, L ¼ Py, 13, Py-d5, 13D] was carried out by mixing com-
pounds 7 or 8 and the corresponding ligand L, under mild condi-
tions, which yielded 11e13, 12D and 13D ranging 51.9e81.3%,
Scheme 5. All compounds are readily soluble in THF, CH2Cl2,
acetone and chloroform. These derivatives were fairly stable in the
solid state at room temperature and hygroscopic.
Further reactivity in solution was observed for complex 7.
Addition of carbon monoxide, at 1 atm, to a solution of 7 in CHCl3 at
~40 ꢁC gave, after 30 min, a deep yellow solution from which 11 was
isolated in 81.3% yield. An IR spectrum in KBr revealed the presence
of a carbonyl ligand in 11 showing a strong band at 1982 cmꢀ1. This
result suggests a higher capability of back-bonding of the CO in
comparison to [Cp*Ru(1,2,5-
h
-CH2CHCRCHSO2)CO] (R ¼ H, 1991;
Me, 1986 cmꢀ1) [15], and [(HMB)Ru(Cl)2CO] (
n
CO, 1996 cmꢀ1) [23].
The reaction of 7 and 8 with pyridine and deuterated pyridine in
CHCl3 or CD3CN solution at room temperature yielded yellow-
orange products 12, 12D, 13 and 13D which were isolated in 73.8,
65.5, 58.4 and 51.9%, respectively. The addition of MeCN or CD3CN
to 7 failed to give stable adducts, namely 14 and 14D. It was possible
to determine by 1H NMR spectroscopy in CD3CN at room temper-
ature that the reaction between 7 and CD3CN was not complete
even after ten days, instead, an equilibrium of 7:14D was observed
Compound 3 exhibited the highest stability in THF-d8 solution
compared to 4 which showed partial transformation in THF-d8
solution to the highly hygroscopic 6, Scheme 2. Isolated compound
6 gave evidence of the partial transformation to compound 4 after
24 h in THF-d8 (see Scheme 2 and Supporting information). The
presence of lithium in 6 was confirmed through the 7Li NMR

112
J.I. de la Cruz-Cruz, M.A. Paz-Sandoval / Journal of Organometallic Chemistry 791 (2015) 107e118
Scheme 5. Synthesis of compounds 11e13 and 12De13D.
in a 1:3 ratio (see Supporting information). The facile dissociation
of CH3CN in 14 compared to CD3CN in 14D, is significantly more
evident. Nevertheless, attempts to isolate 14D failed because of the
lability of CD3CN, and only compound 7 was recovered. The reac-
tion of 8 with CD3CN showed only traces of the corresponding
deuterated adduct. The 1H and 13C NMR spectra of 11e13 and
12De14D displayed some general features and support the char-
acteristic S conformation in the butadienesulfonyl ligand, as
described in Section 2.1.1.1.
Nonetheless the phosphine base adducts were fully characterized
in solid state and in solution. The assignment of 15e17 through 31
{1H} NMR spectroscopy confirms the phosphorus coordination, and
1H and 13C spectroscopy gave evidence of the 1 coordination (e. g.
P
h
1H
d
¼ 5.07, J ¼ 17.2 Hz, H1; 5.10, J ¼ 8.7 Hz, H1'; 8.44, J ¼ 17.2, 10.5,
1.1, H2; 5.81, J ¼ 11.1 Hz, H3; 7.20, J ¼ 11.0 Hz, H4; and 13
C
d
¼ 120.4,
J ¼ 156.8 Hz, C1; 134.0 J ¼ 162.2, 10.8, 3.8 Hz, C2; 128.1 J ¼ 158.4 Hz,
C3; 140.8, J ¼ 172.7 Hz, C4 for compound 15) and the exclusive S
conformation of the butadienesulfonyl ligand as described in Sec-
tion 2.1.1.1 (see Supporting information). The isoelectronic com-
pounds 15Cp*M (M ¼ Rh, Ir; PMe3) and 16Cp*M (M ¼ Rh, Ir; PPh3)
have shown mixtures of isomers, where an S conformation of the
butadienesulfonyl ligand can be transformed to the corresponding
W, by heating the samples in solution [14]. In contrast, compounds
15 and 16 did not show any isomerization after two days in CDCl3
solution even after heating the sample in an oil-bath at 65 ꢁC for
three days. During this treatment, a small quantity of 15Cl was
observed at early stages and reaching a 2:1 ratio of 15:15Cl by the
end of the reaction. This result suggested the presence of the
electron deficient species (HMB)Ru(Cl)(PR3) [24], which can easily
coordinate another chloride, and gives evidence for the relatively
weak rutheniumesulfur bond. A similar trend has been observed in
the reaction mixtures of 15Cp*M and 16Cp*M (M ¼ Rh, Ir) and the
corresponding Cp*M(Cl)2(PR3) (M ¼ Rh, Ir; R ¼ Me, Ph) [14], and in
a mixture of (HMB)Ru(CO)(CH2]CH2), (HMB)Ru(Et)2 and [(HMB)
Ru(I)2(CO)] [25]. Unsuccessful results were obtained in the addition
of phosphines to compound 8 due to the stronger coordination of
the terminal double bond to the ruthenium atom. It should be
mentioned that the metathesis reaction of (HMB)Ru(Cl)2PPh3 and
2K was not useful as a synthetic alternative in the formation of 16.
In contrast to this result, the isoelectronic Cp*M(Cl)2PPh3 (M ¼ Rh,
Ir) reacts with 2K more efficiently to give the corresponding
16Cp*M [14].
The 1H and 13C NMR chemical shifts at the highest frequencies
were observed for 11, where the proton (
ternary carbon (
¼ 112.1) chemical shifts of the HMB ligand re-
flected the low contribution of -acceptor capability of this arene
d
¼ 2.28) and the qua-
d
p
ligand. In general, the quaternary carbon resonances of the HMB
were diagnostic and clearly reflected the contribution of the donor
ligands involved. The
12De14D and alkali-metal derivatives 3e6 showed chemical shifts
for quaternary carbons in the range of
¼ 94.7e98.3, whereas in
complexes 7, 8,10 and 11 more electron deficient quaternary carbon
atoms of the HMB ligands (
¼ 102.8e116.6) were found. An
exception was the chemical shift of 9 (
¼ 103.7), which can be
s-nitrogen donor ligands in 12e13 and
d
d
d
explained due to a second butadienesulfonyl ligand coordinated to
the ruthenium atom. According to these chemical shift values, the
13C NMR spectra were quite useful, as they gave indirect informa-
tion of other ligands coordinated to the ruthenium atom as well. In
addition, both butadienesulfonyl and the butadienesulfinate are
acting as better
in 7e11; while the opposite was observed for the
p
-acceptor ligands than the ancillary arene ligands
-donor adducts.
s
The IR spectra of the neutral compounds 11e13 and 12D, 13D
showed sharp bands, and significant differences in the corre-
sponding stretching S]O frequencies: 11
(nas1201, 1055;
ns1010 cmꢀ1); 12 (nas1162, 1071, 1109; ns1028 cmꢀ1); 12D (nas1163,
1071, 1108; ns1030; cmꢀ1); 13 (nas1194, 1116, 1165; ns1037 cmꢀ1);
13D (nas1189, 1119, 1159; ns1034 cmꢀ1) which was interpreted as
The IR spectra of phosphine derivatives 15e17 showed the
highest wavenumber for the S]O symmetric stretching fre-
quencies, for 16 (ns 1051; nas 1091, 1192 cmꢀ1), while 15 (ns 1040;
nas 1069, 1110, 1168 cmꢀ1) and 17 (ns 1041; nas 1070, 1103, 1178,
the pushepull interplay of the different ligands, that is the
p-
acceptor CO and the -donor nitrogen ligands, according to the
s
stretching vibrations at higher wavenumber in 11 compared to 12
and 13.
cmꢀ1) were quite similar, in spite of the different
s and p-capa-
bilities of the corresponding PMe3 and PHPh2. While electronic
factors may be significant, it is worth noting that the higher cone
angle [26] of the PPh3 ligand (145ꢁ) relative to the PHPh2 (126ꢁ) or
PMe3 (118ꢁ) was sufficient to rationalize the different behavior
observed.
Complex 15 was isolated as an air-stable yellow solid, which was
recrystallized from methylene chloride/hexane at ꢀ30 ꢁC. Adduct
15 crystallizes in an orthorombic system with a space group Pna21
with four molecules in the asymmetric unit and water as solvate.
The molecular structure of 15 is shown in Fig. 2, and full data is
provided in the Supporting information.
2.1.3. Reactivity of Compound 7 with phosphine ligands
The addition reaction of 7 with PMe3 and PHPh2 in THF and PPh3
in benzene at room temperature afforded compounds [(HMB)
Ru(Cl)(5-
h
-CH2CHCHCHSO2)L] (L ¼ PMe3, 15; PPh3, 16 and PHPh2,
17) in 65.6, 67.5 and 49.3% yield, respectively. These compounds in
solution were always accompanied by the formation of the corre-
sponding dichloride derivatives (HMB)Ru(Cl)2L (L ¼ PMe3, 15Cl;
PPh3, 16Cl and PHPh2, 17Cl), Scheme 6.
The 1H and 31P NMR spectra showed each pair of compounds in
a ratio 15:15Cl (14.5:1.0), 16:16Cl (10.5:1.0) and 17:17Cl (10.2:1.0).

J.I. de la Cruz-Cruz, M.A. Paz-Sandoval / Journal of Organometallic Chemistry 791 (2015) 107e118
113
Scheme 6. Synthesis of compounds 15e17 and dichloride derivatives 15Cle17Cl.
The crystaI structure shows a pseudo-octahedral geometry
about the metal center with the HMB ligand occupying three co-
ordination sites, with the other three sites occupied by one chlo-
ride, one trimethylphosphine and one butadienesulfonyl ligands.
The same chemical structure was confirmed in solution and in
solid state, which was supported by the effective intramolecular
[28,29] where the corresponding bond lengths are RueP [2.343(3)
and 2.343(1) Å] and RueCl [2.422(3), 2.424(3) and 2.4181(9) Å]. The
RueS distance [2.2996(11) Å] in 15 can be compared with the
values of 15Cp*M [M ¼ Rh, 2.307(3); Ir, 2.301(3) Å] [14]. According
to the bond lengths of the HMB coordinated ligand to the ruthe-
nium atom [C(5)-Ru(1) 2.291 (4), C(6)-Ru(1) 2.233(4), C(7)-Ru(1)
2.253(4), C(8)-Ru(1) 2.307(3), C(9)-Ru(1) 2.277(4), C(10)-Ru(1)
2.267(4) Å], and in comparison with those of 15Cp*Ir [C(5)-Ru(1)
2.165 (11), C(6)-Ru(1) 2.255(10), C(7)-Ru(1) 2.236(10), C(8)-Ru(1)
2.219(10), C(9)-Ru(1) 2.265(11) Å] it is clear that the (HMB)Ru
interaction observed between H(2) and O(1) [2.3278 Å] of the 5-h-
CH2CHCHCHSO2 coordinated ligand (van der Waals radius of
2.95 Å). A shorter distance was also observed from the intra-
molecular interaction between H(4) and Cl(1), (2.7444 Å) where
van der Waals radius is 3.35 Å. The bond angles of this piano stool
fragment gave evidence of the similar influence of the different
ligands [S(1)-Ru(1)-P(1) 87.35(4)ꢁ, P(1)-Ru(1)-Cl(1) 87.70(4)ꢁ, S(1)-
Ru(1)-Cl(1) 87.49(4)ꢁ]. Comparatively, the (HMB)Ru(Cl)2PMe3 [27]
and (HEB)Ru(Cl)2PMe3 (HEB ¼ Hexaethylbenzene) [28,29] com-
plexes showed less symmetric coordination angles: 82.04(11) and
82.11(3)ꢁ; 84.96(11) and 82.11(3)ꢁ; 90.31(10) and 90.35(5)ꢁ for the
P(1)ꢀRu(1)ꢀCl(1), P(1)ꢀRu(1)ꢀCl(2), and Cl(2)ꢀRu(1)ꢀCl(1) units,
respectively. The torsional angle C1eC2eC3eC4 [ꢀ177.06(1.55)ꢁ]
gave evidence of the S conformation of the butadienesulfonyl
ligand and the planarity reflected by 4.37 (1.03)ꢁ.
moiety has lower
ancillary ligand.
p-acceptor capability compared to the Cp*
3. Conclusions
Representative examples of the butadienesulfonyl and buta-
dienesulfinate ligands with the (HMB)RuCl fragment were syn-
thesized and a comparative study was established with the
analogue isoelectronic complexes 15Cp*M and 16Cp*M
(M ¼ Rh [12,14], Ir [14], and Cp*Ru(1,2,5-
h-butadienesulfonyl)(L)
[15].
The RueP [2.3417(11) Å] and RueCl [2.4151(11) Å] bond lengths
were in the expected range of typical mixed half-sandwich com-
pounds, such as (HMB)Ru(Cl)2PMe3 [27] and (HEB)Ru(Cl)2PMe3
The thermodynamic stability of the (HMB)Ru(Cl)(1,2,5-
h-buta-
dienesulfonyl) and (HMB)Ru(Cl)(5- -butadienesulfonyl)(L) com-
h
plexes is attributed, in part, to the steric bulk and electron-donating
properties of the HMB ligand. In contrast, and as expected, the
presence of the butadienesulfinate complexes in 3e6 and 9 induce
low thermal stability, with 3 and 9 being the most stable at room
temperature. Our preliminary experience with the Cp*M moieties
(M ¼ Ru [11], Rh [12,14], Ir [13,14]) and the butadienesulfinate and
butadienesulfonyl ligands indicated that the latter ligand is less
prone to hydrolysis compared to the (HMB)Ru derivatives, where
even neutral derivatives 7, 8, 10e17 were found to be hygroscopic in
the presence of traces of water. In the chemistry of the (HMB)Ru
complexes it was possible to detect, at least spectroscopically, the
potassium complex 5, while no evidence of potassium derivatives
was observed in the corresponding chemistry with the Cp*M
(M ¼ Ru, Rh, Ir) moiety.
The reactivity of 7 and 8 showed a strong reaction dependence
on the nature of the substituent at the central carbon atom (C3) in
the presence of nitrogen donor ligands and their corresponding
deuterated analogues. The methyl group substituted in the buta-
dienesulfonyl ligand of compound 8 favored equilibrium reactions.
The previous synthetic methods which have been exploited in
the Cp*Ru(heteropentadienyl) [3e5,30] chemistry were not useful
in the development of the analogous chemistry of the (HMB)Ru
moiety [8,9].
Fig. 2. Molecular structure of [(HMB)Ru(Cl) (5-h-CH2CHCHCHSO2)PMe3] (15). Thermal
ellipsoids at the 45% probability level. Selected bond distances (Å): C1eC2, 1.342(8);
C2eC3, 1.435(8); C3eC4, 1.323(7); C4eS1, 1.794(5); S1eO1, 1.455(3); S1eO2, 1.462(4);
Ru1eS1, 2.2996(11); Ru1eP1, 2.3417(11); Ru1eCl1, 2.4151(11); P1eC13, 1.818(5).
Selected bond angles (ꢁ): S1eRu1eCl1, 87.49(4); P1eRu1eCl1, 87.70(4); S(1)-Ru(1)-
P(1) 87.35(4); C1eC2eC3, 124.7(6); C2eC3eC4, 130.4(5); C3eC4eS1, 128.4(4).
HMB(centroid)-Ru, 1.7684 Å.
More extensive exploration of the chemistry of these dioxo-

114
J.I. de la Cruz-Cruz, M.A. Paz-Sandoval / Journal of Organometallic Chemistry 791 (2015) 107e118
sulfur-based ligands with other transition metals may be of special
interest because of their potential relevance in biological and syn-
thetic processes, and current work in our laboratory is focused on
the study of the cationic complexes [(HMB)Ru(1-5-h-
CH2CHCRCHSO2)][X] (R ¼ H, Me; X ¼ BF4, OTf).
1.70, 3.55 (s, THF), 1.75, 3.59 (m, THF). 7Li NMR (194 MHz, THF-d8)
d
¼ 0.17 (s, br). 13C{1H} NMR (125 MHz, THF-d8)
¼ 115.1 (C1), 134.6
d
(C2), 132.8 (C3), 18.2 (Me3), 137.4 (C4), 95.0 (C6Me6), 14.5 (C6Me6),
24.4, 66.5 (quintet, THF), 25.5, 67.3 (s, THF). IR(KBr): 3023(w),
2914(s), 2863(m,sh), 2725(w,br), 2384(w,br), 2216(w,br),
1948(w,br), 1844(w,br), 1763(w,br), 1637(vs), 1575(s), 1439(vs),
1384(vs), 1251(w), 1154(vs), 1124(vs), 1021(vs,br), 922(m,sh),
835(s), 778(m,sh), 701(m,sh), 615(vs,br), 546(vs,br), 502(vs,br).
4. Experimental section
Standard inert-atmosphere techniques were used for all syn-
thetic procedures. The solvents were dried by standard methods
(hexane and pentane with CaH2 and THF with Na/benzophenone.
CH2Cl2 and CHCl3 with CaCl2, benzene and toluene with Na, CH3CN
4.2. Identification of [(HMB)Ru(Cl)2(5-h-
CH2CHCHCHSO2)(K)(THF)]2 (5)
with P2O5) and distilled under argon prior to use. Compounds [(h6
-
An NMR tube containing 30.0 mg (0.045 mmol) of 1 and 14.0 mg
(0.09 mmol) of 2K in THF-d8 was monitored by 1H NMR for 24 h. 1H
p-cymene)Ru(m-Cl)Cl]2 [31], [(HMB)Ru(m-Cl)Cl]2 (1) [31b] and the
salts (CH2CHCRCHSO2M) (M ¼ Li, R ¼ H, 2Li; M ¼ Li, R ¼ Me,
2LieMe; M ¼ K, R ¼ H, 2K; M ¼ K, R ¼ Me, 2KeMe) [21] were
prepared according to literature procedures. All other chemicals
were used as purchased from Pressure Chemical, SigmaeAldrich,
Strem Chemical, Merck, and J. T. Baker (industrial grade). All com-
pressed gases were obtained from Infra. Argon (>99.9%), nitrogen
(>99.5%) and carbon monoxide (>99.5%) were used as supplied
without purification. IR spectra were recorded using KBr pellets
NMR (500 MHz, THF-d8)
d
¼ 5.15 (d, J ¼ 15.6 Hz, H1), 5.12 (d,
J ¼ 8.6 Hz, H10), 8.03 (dt, J ¼ 10.4, 17.2 Hz, H2), 5.84 (t, J ¼ 11.2 Hz,
H3), 6.37 (d, J ¼ 11.3 Hz, H4), 1.94 (s, C6Me6), 1.70, 3.56 (s, THF). 13
C
{1H} NMR (125 MHz, THF-d8) (in mixture with 7 and 9, vide supra)
d
¼ 119.3 (C1), 133.7 (C2), 127.1 (C3), 141.0 (C4), 94.7 (C6Me6), 14.6
(C6Me6), 24.2, 66.7 (quintet, THF).
4.3. Synthesis of [(HMB)Ru(Cl)2(5-h-CH2CHCMeCHSO2Li)] (6)
(4000e400 cmꢀ1). Melting points are uncorrected. The 1H, 13C, 13
C
{1H}, 31P{1H} and 7Li NMR spectra are referenced internally using
the residual protio and carbon solvent resonances relative to tet-
ramethylsilane with deoxygenated deuterated solvents. External
standard for 31P was H3PO4 and LiCl/H2O (9.7 mM) for 7Li. Routine
2-D sequences in NMR were used for all assignments. High-
resolution mass spectra were obtained by LC/MSD TOF with APCI
as ionization source. LR/FAB Finnigan MAT95 (FAB)þ mass spec-
trometer. Elemental analyses were performed in the Chemistry
Department at Cinvestav.
Compound 8 (47.0 mg, 0.109 mmol) and 7.0 mg of LiCl
(0.164 mmol) were placed into a Schlenk flask equipped with a stir
bar and the mixture was left under vacuum for 5 min at room
temperature. THF (10 mL) was added and gave a yellow-orange
solution which turned amber after stirred 50 min at room tem-
perature. After filtration, the THF was reduced under vacuum to
~2 mL, and pentane was added in order to induce precipitation of
an orange solid, which was filtered, rinsed with pentane (2 ꢂ 5 mL),
filtered again, and dried under vacuum. This afforded a yellow-
orange compound 6 in 62.4% (31.2 mg, 0.068 mmol) which mel-
ted at 92e94 ꢁC with decomposition. 6 was unstable at room
temperature and was also quite hygroscopic. Compound 6: 1H NMR
4.1. General method for the synthesis of [(HMB)Ru(Cl)2(5-h-
CH2CHCRCHSO2)(Li)(THF)]2 [R ¼ H, 3; Me, 4]
(500 MHz, THF-d8)
d
¼ 5.30 (d, J ¼ 17.5 Hz, H1), 5.17 (d, J ¼ 11.9 Hz,
Compound 1 (150 mg, 0.224 mmol) and the corresponding
lithium salt 2Li (84.0 mg, 0.677 mmol) or 2LieMe (144.0 mg,
1.043 mmol) were placed into a Schlenk flask equipped with a stir
bar and the mixture was left under vacuum for 5 min. THF (50 mL)
was added, and the mixture was stirred for 2h, changing from
orangeebrick to brown-amber. The THF solution was filtered
through Celite (2.5 ꢂ 3.5 cm) before the resulting brown-amber
filtrate was cannula filtered to a Schlenk flask. The THF was
reduced under vacuum to ~3 mL, and pentane was added. After
stirring this solution, a light-brown or dark-beige precipitate,
respectively, appeared. The solid was filtered, rinsed with pentane
(5 mL) and dried under vacuum affording compounds 3 (127.0 mg,
0.120 mmol, 53%) and 4 (98.0 mg, 0.090 mmol, 40%). Compounds 3
and 4 did not melt until 300 ꢁC, and decomposed at 170 ꢁC and
142 ꢁC, respectively. Compound 3: 1H NMR (500 MHz, THF-d8)
H10), 8.26 (dd, J ¼ 10.9, 17.8 Hz, H2), 1.87 (s, Me3), 6.46 (s, H4), 1.98
(s, C6Me6). 7Li (194 MHz, THF-d8) NMR
d
¼ 0.21 (s). 13C{1H} NMR
(125 MHz, THF-d8)
d
¼ 115.2 (C1), 134.6 (C2), 132.9 (C3), 18.2 (Me3),
137.4 (C4), 95.0 (C6Me6),14.6 (C6Me6). 1H NMR (500 MHz, (CD3)2CO)
d
¼ 5.37 (dd, J ¼ 0.9, 17.7 Hz, H1), 5.22 (dt, J ¼ 1.6, 10.9 Hz, H10), 8.16
(dd, J ¼ 10.9, 17.7 Hz, H2), 1.88 (d, J ¼ 1.2 Hz, Me3), 6.32 (s, H4), 1.98
(s, C6Me6). 7Li NMR (194 MHz, (CD3)2CO)
(125 MHz, (CD3)2CO)
d
¼ 1.29 (s). 13C{1H} NMR
d
¼ 116.5 (C1), 134.0 (C2), 134.1 (C3), 18.4
(Me3), 137.0 (C4), 95.3 (C6Me6), 14.8 (C6Me6). ESI-TOF: m/z
561.0469, error: 0.172732 ppm, DBE: 6.5, (see Scheme 4). IR(KBr):
2043(w,br), 1706(sh), 1634(vs,br), 1438(s,br), 1385(s,br), 1287
(w,br), 1253(w,br), 1152(s,br), 1124(sh), 1031(vs,br), 926(sh),
839(s,br), 724(w,br), 616(w,br), 497(w,br). Anal Calcd for
C17H25Cl2LiO2RuS,2H2O (508.40): C, 40.16; H, 5.75. Found: C, 40.11;
H, 5.79.
d
¼ 5.18 (d, J ¼ 17.0 Hz, H1), 5.15 (d, J ¼ 10.2 Hz, H10), 8.00 (dt,
J ¼ 10.6, 17.0 Hz, H2), 5.89 (t, J ¼ 11.1 Hz, H3), 6.46 (d, J ¼ 11.3 Hz,
4.4. General method for the synthesis of [(HMB)Ru(Cl)(1,2,5-h-
CH2CHCRCHSO2)] [R ¼ H, 7; Me, 8]
H4), 1.96 (s, C6Me6), 1.71, 3.56 (s, THF), 1.75, 3.59 (m, THF). 7Li NMR
(194 MHz, THF-d8)
d
d
¼ 0.18 (s, br). 13C{1H} NMR (125 MHz, THF-d8)
¼ 119.8 (C1), 133.5 (C2), 128.6 (C3), 138.2 (C4), 95.0 (C6Me6), 14.5
Compound 1 (150 mg, 0.224 mmol) and the corresponding
potassium salt 2K (70.0 mg, 0.448 mmol) or 2KeMe (92.0 mg,
0.540 mmol) were placed into a Schlenk flask equipped with a stir
bar and the mixture was left under vacuum for 5 min CHCl3 (40 mL)
was added, and the mixture was stirred for 1h or 30 min, respec-
tively, changing from orangeebrick to yellow-orange or yellow-
apple. The solution was filtered through Celite (2.5 ꢂ 3.5 cm)
before the peach-yellow or brilliant-tangerine filtrate was cannula
filtered to a Schlenk flask. The chloroform was reduced under
vacuum to ~3 mL, and pentane was added; after stirring the
(C6Me6), 25.5, 67.3 (s, THF), 24.4, 67.5 (quintet, THF). IR(KBr):
3081(w), 2916(s,br), 2730(w,br), 2448(w,br), 2047(w,br),
1963(w,br), 1846(w,br), 1748(w,br), 1627(s), 1572(s), 1445(s),
1384(vs), 1293(w), 1236(w), 1147(vs), 1104(vs), 1071(vs,sh),
1016(vs,br), 918(s), 819(w), 786(m), 722(w), 672(vs), 551(s), 474(s).
Anal Calcd for C40H62Cl4Li2O4Ru2S2,4H2O (1132.93): C, 42.41; H,
6.23. Found: C, 42.11; H, 6.32. Compound 4: 1H NMR (500 MHz,
THF-d8)
d
¼ 5.27 (d, J ¼ 17.5 Hz, H1), 5.13 (d, J ¼ 11.0 Hz, H10), 8.23
(dd, J ¼ 10.8, 17.7 Hz, H2), 1.83 (s, Me3), 6.43 (s, H4), 1.95 (s, C6Me6),

J.I. de la Cruz-Cruz, M.A. Paz-Sandoval / Journal of Organometallic Chemistry 791 (2015) 107e118
115
solution, a yellow-orange or orange precipitate appeared. The solid
was filtered, rinsed with pentane (2 ꢂ 5 mL) and dried under
vacuum, thus affording compounds 7 (101.0 mg, 0.243 mmol, 54%)
and 8 in (88.0 mg, 0.205 mmol, 46%). Compounds 7 and 8 did not
melt until 300 ꢁC, and decomposed at 185 ꢁC and 190 ꢁC, respec-
an additional 1 h, in order to afford a lemon-yellow suspension. The
solution was filtered and the solvent removed until dryness. The
solid residue was dissolved in CHCl3 (5 mL), stirred 5 min and
filtered; then the solution evaporated until dryness, in order to give
a yellow-beige solid in 53.4% (23.2 mg, 0.047 mmol). This solid
decomposed at 173 ꢁC, without melting below 250 ꢁC. Compound
tively. Compound 7: 1H NMR (400 MHz, CDCl3)
d
¼ 3.61 (d, J ¼ 13.3
Hz, H1), 3.73 (d, J ¼ 9.7 Hz, H10), 5.04 (dd, J ¼ 10.0, 11.5 Hz, H2), 5.86
10: 1H NMR (500 MHz, CDCl3)
d
¼ 3.13 (d, J ¼ 12.4 Hz, H1a), 5.33 (d,
(t, J ¼ 6.3 Hz, H3), 6.40 (d, J ¼ 6.3 Hz, H4), 2.12 (s, C6Me6). 13C NMR
J ¼ 16.3 Hz, H1b), 3.43 (d, J ¼ 9.2 Hz, H1'a), 5.32 (d, J ¼ 8.1 Hz, H1'b),
4.88 (t, J ¼ 10.8 Hz, H2a), 7.64 (dt, J ¼ 11.0, 16.3 Hz, H2b), 6.01 (d,
J ¼ 6.0 Hz, H3a), 5.96 (t, J ¼ 11.0 Hz, H3b), 6.29 (d, J ¼ 6.0 Hz, H4a),
6.47 (d, J ¼ 10.6 Hz, H4b), 2.20 (s, C6Me6). 13C{1H} NMR (125 MHz,
(100 MHz, CDCl3)
d
¼ 67.2 (dd, J ¼ 157.3, 166.9 Hz, C1), 91.0 (ddd,
J ¼ 158.8, 8.6, 4.8 Hz, C2), 129.9 (dap, J ¼ 160.3 Hz, C3), 154.8 (dt,
J ¼ 180.4, 4.8 Hz, C4), 108.2 (s, C6Me6), 15.5 (q, 128.8 Hz, C6Me6).
ESI þ TOF: m/z 417.0225; error: 0.3508, DBE: 4.5. IR(KBr): 3040(w),
2927(w), 2865(w), 2612(w,br), 2180(w,br), 1743(w,br), 1662(w,br),
1625(w,br), 1452(m,br), 1386(s), 1290(m), 1264(w,sh), 1187(vs),
1111(m,sh), 1080(s,sh), 1047(vs), 966(w,sh) 808(m), 741(m),
656(m), 631(m), 538(s), 445(m). Anal Calcd for C16H23ClO2RuS
(415.95): C, 46.20; H, 5.57. Found: C, 45.94; H, 5.20. Compound 8: 1H
CDCl3)
d
¼ 62.5, (C1a), 124.1 (C1b), 87.1 (C2a), 131.4 (C2b), 130.3
(C3a), 132.2 (C3b), 152.5 (C4a), 135.7 (C4b), 116.6 (C6Me6), 16.4
(C6Me6). ESI þ TOF: m/z 499.054559, error: 0.063640 ppm, DBE:
6.5. IR(KBr): 3056(w,br), 3001(w,br), 2926(m,br), 2863(w,br),
2608(w,br), 2379(w,br), 2214(w,br), 1966(w,br), 1723(m,br),
1627(s), 1571(m), 1448(m,br), 1386(s), 1293(m), 1179(vs,br),
1112(s,br), 1046(vs,br), 931(m,sh), 803(m), 744(m), 665(s), 540(s),
475(m). Anal Calcd for C20H28O4RuS2,0.5CHCl3 (557.33): C, 44.18;
H, 5.15. Found: C, 44.09; H, 5.38.
NMR (400 MHz, CDCl3)
d
¼ 3.72 (d, J ¼ 13.4 Hz, H1), 3.71 (d,
J ¼ 9.2 Hz, H10), 5.13 (dd, J ¼ 9.9, 13.1 Hz, H2), 1.96 (s, Me3), 6.20 (s,
H4), 2.11 (s, C6Me6). 13C{1H} NMR (100 MHz, CDCl3)
d
¼ 65.8 (C1),
93.4 (C2), 141.5 (C3), 19.6 (Me3), 149.2 (C4), 108.2 (C6Me6), 15.5
(C6Me6). ESI þ TOF: m/z 431.0379; error: ꢀ0.1827, DBE: 4.5. IR(KBr):
3025(w), 2969(w), 2911(w), 2863(w), 2347(w,br), 2273(w,br),
1947(w,br), 1640(m), 1439(s), 1386(s), 1250(w), 1182(vs), 1118(s),
1071(s,sh), 1043(vs), 823(m), 775(w), 540(m), 500(m). Anal Calcd
for C17H25ClO2RuS,0.5H2O (438.97): C, 46.52; H, 5.97; S, 7.30.
Found: C, 46.51; H, 5.31; S, 7.40.
4.7. Synthesis of [(HMB)Ru(Cl)(5-h-CH2CHCHCHSO2)(CO)] (11)
Compound 7 (53.0 mg, 0.127 mmol) was placed into a glass
reactor equipped with a stir bar under vacuum for 5 min at room
temperature. CHCl3 (15 mL) was added, and then CO was intro-
duced at 1 atm. The reaction mixture was warmed in an oil bath
and stirred at 55e60 ꢁC (~40 ꢁC) for 30 min. The solution turned
from bright-yellow to deep-yellow. After replacement of CO by an
argon atmosphere, the solution was filtered and the volume of
CHCl3 was reduced to ~3 mL; pentane was added in order to induce
the precipitation of a deep yellow solid, which was filtered, rinsed
with 5 mL of pentane, filtered again, and dried under vacuum for
2 h. Compound 11 was obtained in 81.3% (46.0 mg, 0.104 mmol); it
decomposed at 183 ꢁC, without melting below 300 ꢁC. Compound
4.5. Synthesis of [(HMB)Ru(Cl)(5-
CH2CHCHCHSO2K)] (9)
h-CH2CHCHCHSO2)(5-h-
Compound 7 (117.0 mg, 0.281 mmol) and the corresponding
potassium salt 2K (470.0 mg, 3.01 mmol) were placed into a
Schlenk flask equipped with a stir bar and the mixture was left
under vacuum for 5 min and the temperature stabilized at 20 ꢁC.
THF (50 mL) was added, and the mixture was stirred 21 h at this
temperature. The solution was filtered through Celite (2.5 ꢂ 3.5 cm)
and the yellow-orange solution was filtered again with a cannula to
a Schlenk flask. The THF was reduced under vacuum to ~3 mL, and
pentane was added; after stirring this solution, a light-yellow
precipitate appeared. The cream-yellow solid was filtered, rinsed
with pentane (2 ꢂ 3 mL) and dried under vacuum to afford com-
pound 9 in 65.3% (105.0 mg, 0.184 mmol) which decomposes at
11: 1H NMR (500 MHz, CDCl3)
d
¼ 5.33 (dap, J ¼ 16.9 Hz, H1), 5.31
(dap, J ¼ 10.1 Hz, H10), 7.64 (m, J ¼ 1.1, 10.7, 17.0 Hz, H2), 6.05 (t,
J ¼ 11.1 Hz, H3), 6.53 (dd, J ¼ 0.8, 11.0 Hz, H4), 2.28 (s, C6Me6). 13
C
NMR (125 MHz, CDCl3)
d
¼ 123.9 (tap, J ¼ 158.4, 5.8 Hz, C1), 131.7
(ddd, J ¼ 162.7, 10.1, 3.8 Hz, C2),132.1 (tap, J ¼ 154.5 Hz, C3), 139.3 (d,
J ¼ 175.6 Hz, C4), 112.1 (s, C6Me6), 16.5 (Hz q, 130.0, C6Me6), 195.5 (s,
CO). ESI þ TOF: m/z 445.0174, error: 0.2509 ppm, DBE: 5.5. IR(KBr):
2925(m,br), 2068(m), 1982(vs), 1625(w), 1572(m), 1444(m,br),
1385(s), 1201(vs), 1055(vs), 1010(m,sh), 928(m), 780(s), 723(m),
669(vs), 636(s), 535(s), 477(m). Anal. Calcd for C17H23ClO3RuS,H2O
(461.96): C, 44.20; H, 5.45; S, 6.94. Found: C, 44.21; H, 5.06; S, 6.70.
210 ꢁC. Compound 9: 1H NMR (500 MHz, CDCl3)
d
¼ 5.27 (d, J ¼ 17.0
Hz, H1), 5.26 (d, J ¼ 9.9 Hz, H10), 7.74 (dt, J ¼ 10.7, 16.3 Hz, H2), 5.94
(t, J ¼ 11.1 Hz, H3), 6.48 (d, J ¼ 11.0 Hz, H4), 1.98 (s, C6Me6). 13C NMR
(125 MHz, CDCl3)
d
¼ 122.6 (t, J ¼ 156.4 Hz, C1), 132.7 (dd, J ¼ 161.7,
9.1 Hz, C2), 129.6 (dap, J ¼ 154.5 Hz, C3), 139.5 (d, J ¼ 172.7 Hz, C4),
103.7 (s, C6Me6), 15.8 (q, J ¼ 128.8 Hz, C6Me6). ESI-TOF: m/z
533.0167, error: 0.0898 ppm, DBE: 6.5. IR(KBr): 3082(w), 3043(w),
3000(w), 2923(m), 2345(vw), 2169(w,br), 1966(w,br), 1847(w,br),
1709(w,br), 1627(m,br), 1571(m), 1440(m,br), 1385(m), 1307(m,br),
1156(vs), 1110(s,sh), 1039(vs), 918(m), 789(m), 715(w), 664(vs),
543(s), 474(m). Anal Calcd for C20H28ClKO4RuS,H2O (590.19): C,
40.70; H, 5.12. Found: C, 40.96; H, 5.26.
4.8. Synthesis of [(HMB)Ru(Cl)(5-h-CH2CHCHCHSO2)(C5H5N)] (12)
Compound 7 (50.0 mg, 0.120 mmol) was placed into a Schlenk
flask equipped with a stir bar under vacuum for 5 min at room
temperature. CHCl3 (10 mL) was added, followed by 10.0
pyridine (9.51 mg, 0.120 mmol). The mixture was stirred for 1.2 h at
room temperature changing from yellow to orange. After filtration,
the CHCl3 was reduced under vacuum to ~2 mL; pentane was added
in order to induce precipitation of a yellow-orange solid, which was
filtered, rinsed with pentane (2 ꢂ 3 mL), filtered again, and dried
under vacuum. This afforded compound 12 in 73.8% (43.9 mg,
0.089 mmol) which melted with decomposition at 163e164 ꢁC.
mL of
4.6. Synthesis of [(HMB)Ru(1,2,5-h-CH2CHCHCHSO2)(5-h-
CH2CHCHCHSO2)] (10)
Compound 9 (50.0 mg, 0.087 mmol) and AgBF4 (17.0 mg,
0.087 mmol) were placed into a Schlenk flask equipped with a stir
bar; the solid mixture was left under vacuum for 5 min, then it was
cooled at ꢀ110 ꢁC (N2liq/EtOH). Acetone (5 mL) was added, and the
cooling bath was removed 5 min later, whereupon the resulting
yellow solution was stirred until it reached room temperature plus
Compound 12: 1H NMR (500 MHz, CD3CN)
d
¼ 5.01 (m, J ¼ 17.1 Hz,
H1), 5.11 (m, J ¼ 10.1 Hz, H10), 7.64 (dt, J ¼ 11.0, 17.3 Hz, H2), 5.48 (t,
J ¼ 11.1 Hz, H3), 5.65 (d, J ¼ 11.4 Hz, H4), 1.89 (s, C6Me6), 8.85 (d, 5.0,
1.4 Hz, H
NMR (125 MHz, CD3CN)
(C4), 97.7 (C6Me6), 14.6 (C6Me6), 155.1 (C
a), 7.37 (m, 7.6, 6.7 Hz, Hb), 7.80 (tt, 7.7, 1.6 Hz, Hg
). 13C{1H}
d
¼ 120.8 (C1), 132.6 (C2), 129.3 (C3), 138.5
a
), 125.3 (C ), 137.9 (C ).
b
g

116
J.I. de la Cruz-Cruz, M.A. Paz-Sandoval / Journal of Organometallic Chemistry 791 (2015) 107e118
ESI þ TOF: m/z ¼ 496.064604; error: 0.1030; DBE: 7.5. IR(KBr):
3065(m), 3037(m), 2985(m), 2922(m), 2454(w,br), 2044(w,br),
1850(w,br), 1627(w), 1603(w), 1568(m), 1483(m), 1449(s), 1385(s),
1289(w), 1222(w), 1162(vs), 1109(m), 1071(vs), 1028(vs), 921(m),
770(s), 704(s), 660(vs), 537(m), 469(m). Anal. Calcd for
isolated in 51.9% yield (24.8 mg, 0.05 mmol). This solid melted with
decomposition at 172e174 ꢁC. Compound 13D: 1H NMR (500 MHz,
CDCl3)
d
¼ 5.11 (d, J ¼ 17.0 Hz, H1), 5.12 (d, J ¼ 10.6 Hz, H10), 7.89 (dd,
J ¼ 11.0, 16.6 Hz, H2), 1.41 (s, Me3), 5.72 (s, H4), 1.98 (s, C6Me6). 13
C
{1H} NMR (125 MHz, CDCl3)
d
¼ 116.8 (C1), 133.9 (C2), 135.9 (C3),
C
21H28ClNO2RuS$H2O (513.05580): C, 49.16; H, 5.89; N, 2.73. Found:
19.0 (Me3), 137.0 (C4), 97.7 (C6Me6), 15.4 (C6Me6), 154.8 (t, J ¼ 27.8
C, 49.08; H, 5.84; N, 2.34.
Hz, C
a
), 124.5 (t, J ¼ 25.0 Hz, C
b
), 137.0 (t, J ¼ 25.0 Hz, C ). ESI þ TOF:
g
m/z ¼ 515.112011, error: ꢀ0.2504 ppm. IR(KBr): 2015(m), 225(md),
1570(m), 1441(m), 1384(mf), 1319(md), 1189(f), 1159(f), 1119(md),
1034(f), 917(m), 827(m), 729(f), 645(md), 613(mf), 543(mf),
504(m). Anal. Calcd for C22H25D5ClNO2RuS (514.10): C, 51.40; H,
4.90; N, 2.72. Found; C, 50.88; H, 5.19; N, 2.62.
4.9. Synthesis of [(HMB)Ru(Cl)(5-
(12D)
h-CH2CHCHCHSO2)(C5D5N)]
The synthesis was carried out in an NMR tube, using 7 (55.0 mg,
0.13 mmol) and 11.7 L of Py-d5 (12.2 mg, 0.15 mmol) in deuterated
m
acetonitrile (1.2 mL); the mixture was stirred for 1h, filtered and the
CD3CN evaporated. The solid was rinsed with pentane (2 ꢂ 5 mL),
filtered and dried under vacuum. The yellow-orange solid was
obtained in 65.5% yield (43.3 mg, 0.087 mmol). Compound 12D
melted with decomposition at 163e165 ꢁC. Compound 12D: 1H
4.12. Identification of [(HMB)Ru(Cl)(5-h-CH2CHCHCHSO2)(CD3CN)]
(14D)
The synthesis was carried out in an NMR tube, using 7 (30.0 mg,
0.07 mmol) and excess of CD3CN (0.6 mL). The orange solution was
monitored through the 1H NMR, showing that after 1h and even
after 10 days a 1:3 ratio (7:14D) remained in the CD3CN solution.
NMR (500 MHz, CDCl3)
d
¼ 4.97 (d, J ¼ 17.3 Hz, H1), 5.07 (d,
J ¼ 10.2 Hz, H10), 7.66 (dt, J ¼ 10.6, 17.0 Hz, H2), 5.51 (t, J ¼ 11.3 Hz,
H3), 5.75 (d, J ¼ 11.3 Hz, H4),1.95 (s, C6Me6). 13C{1H} NMR (125 MHz,
Compound 14D: 1H NMR (500 MHz, CD3CN)
d
¼ 5.21 (m, J ¼ 17.0 Hz,
CDCl3)
d
¼ 121.6 (C1),132.4 (C2),130.9 (C3),137.6 (C4), 97.8 (C6Me6),
H1), 5.18 (m, J ¼ 10.7 Hz, H10), 7.63 (m, J ¼ 17.2, 10.6, 1.2, 1.0 Hz, H2),
5.91 (tap, J ¼ 11.2 Hz, H3), 6.11 (m, J ¼ 11.2, 1.9, 1.2 Hz, H4), 2.03 (s,
15.4 (C6Me6), 154.6 (t, J ¼ 28.3, C
a
), 124.7 (t, J ¼ 25.4, C
b), 137.1 (t,
J ¼ 25.0 Hz, C
g). ESI þ TOF: m/z ¼ 501.096585; error: 0.1895.
C6Me6). 13C{1H} NMR (125 MHz, CD3CN)
d
¼ 121.1 (C1), 132.7 (C2),
IR(KBr): 2921(m), 2283(d), 1626(d), 1562(m), 1443(m), 1385(mf),
1320(m), 1163(f), 1108(m), 1071(m), 1030(f), 920(m), 840(md),
780(m), 712(d), 661(f), 542(mf), 471(d). Anal. Calcd for
129.6 (C3), 139.4 (C4), 98.3 (C6Me6), 15.0 (C6Me6), 0.5 (CD3CN), 117.5
(CD3CN).
C
21H23D5ClNO2RuS,H2O (518.09): C, 48.69; H, 4.86; N, 2.70; S, 6.19.
4.13. Synthesis of [(HMB)Ru(Cl)(5-h-CH2CHCHCHSO2)(PMe3)] (15)
Found; C, 48.79; H, 5.52; N, 2.66; S, 6.26.
Compound 7 (58.0 mg, 0.140 mmol) was placed into a Schlenk
flask equipped with a stir bar under vacuum for 5 min at room
temperature. THF (10 mL) was added, followed by 14.4 mL of PMe3
4.10. Synthesis of [(HMB)Ru(Cl)(5-
(13)
h-CH2CHCMeCHSO2)(C5H5N)]
(10.61 mg, 0.14 mmol); the mixture was stirred 2h. After filtration,
the THF was reduced under vacuum to ~1 mL, and cold pentane was
added in order to induce the precipitation of a yellow-orange solid,
which was filtered, rinsed with 2 mL of cold pentane, filtered again,
and dried under vacuum in order to afford compound 15 in 65.6%
(45.0 mg, 0.09 mmol), which melted at 90e93 ꢁC, with decompo-
sition. Compound 15 with traces of 15Cl (15:15Cl, 14.5:1.0): 1H NMR
The synthesis was carried out using 8 (40.0 mg, 0.09 mmol) and
11.3 L of Py (11.0 mg, 0.14 mmol) in CD3CN (1.2 mL) and stirred in a
Vortex for 2h in an NMR tube, followed by a new addition of 3.8
m
mL
of Py (3.68 mg, 0.05 mmol) and stirring for 1 h. The solution was
transferred into a Schlenk tube, and after filtration, evaporation of
CD3CN and washing with pentane (2 ꢂ 5 mL), a yellow-orange solid
was isolated in 58.4% yield (27.7 mg, 0.054 mmol). 13 melts with
decomposition at 173e174 ꢁC. Compound 13: 1H NMR (500 MHz,
(500 MHz, C6D6)
d
¼ 5.07 (d, J ¼ 17.2 Hz, H1), 5.10 (d, J ¼ 8.7 Hz, H10),
8.44 (dtap, J ¼ 17.2, 10.5, 1.1 Hz, H2), 5.81 (t, J ¼ 11.1 Hz, H3), 7.20 (d,
CDCl3)
d
¼ 5.10 (d, J ¼ 17.3 Hz, H1), 5.11 (d, J ¼ 11.7 Hz, H10), 7.89 (dd,
J ¼ 11.0 Hz, H4), 1.71 (s, C6Me6), 1.39 (d, J ¼ 10.6 Hz, PMe3), 31P{1H}
J ¼ 11.0, 17.1 Hz, H2), 1.40 (s, Me3), 5.71 (s, H4), 1.96 (s, C6Me6), 8.97
NMR (202 MHz, C6D6)
d
¼ 6.8 (s). 13C NMR (125 MHz, C6D6)
(d, 5.3 Hz, H
a
), 7.72 (t, 7.6 Hz, H
b
), 7.29 (t, 6.9 Hz, H
g
). 13C NMR
d
¼ 120.4 (tap, J ¼ 156.8, 5.4 Hz, C1), 134.0 (ddd, J ¼ 162.2, 10.8,
(125 MHz, CDCl3)
d
¼ 116.8 (dd, J ¼ 156.9, 156.9 Hz, C1), 134.6 (tap
3.8 Hz, C2), 128.1 (d, J ¼ 158.4 Hz, C3), 140.8 (d, J ¼ 172.7 Hz, C4),
102.8 (s, C6Me6), 15.9 (q, J ¼ 129.1 Hz, C6Me6), 16.8 (q, J ¼ 129.9 Hz,
PMe3). ESI þ TOF (C19H32O2NaPSClRuþ): m/z ¼ 515.0487; error:
0.3862; DBE: 3.5. IR(KBr): 2041(w,br), 1628(m,br), 1571(m),
1427(m,br), 1385(s), 1283(m), 1168(vs), 1110(m), 1069(m,sh),
1040(vs), 959(vs), 857(w), 787(m), 732(m), 661(vs), 540(m),
470(m). Anal. Calcd for C19H32ClO2PRuS (492.02): C, 46.38; H, 6.56;
S, 6.52. Found: C, 45.99; H, 6.76; S, 5.99.
J ¼ 167.5 Hz, C2), 135.9 (s, C3), 19.0 (q, J ¼ 127.6 Hz, Me3), 137.0 (dd,
J ¼ 170.8, 6.7, 4.8 Hz, C4), 97.7 (s, C6Me6), 15.4 (q, J ¼ 129.6 Hz,
C6Me6), 155.2 (d, J ¼ 185.2 Hz, C
a), 125.0 (dt, J ¼ 167.0, 6.7 Hz, C
b),
137.4 (dt, J ¼ 165.1, 6.7 Hz, C ). ESI þ TOF: m/z ¼ 510.079752, error:
g
0.7849, DBE: 7.5. IR(KBr): 3025(m), 2917(m), 1602(d), 1573(md),
1448(mf), 1384(mf), 1194(m), 1165(f), 1116(m), 1037(f), 910(m),
833(m), 768(m), 705(m), 655(d), 609(f), 544(m), 506(m). Anal.
Calcd for C22H30ClNO2RuS (509.07): C, 51.91; H, 5.94; N, 2.75.
Found; C, 51.68; H, 6.01; N, 2.63.
4.14. Synthesis of [(HMB)Ru(Cl)(5-
and [(HMB)Ru(Cl)2(PPh3)] (16Cl)
h-CH2CHCHCHSO2)(PPh3)] (16)
4.11. Synthesis of [(HMB)Ru(Cl)(5-h-CH2CHCMeCHSO2)(C5D5N)]
(13D)
Compound 7 (50.0 mg, 0.120 mmol) and PPh3 (47.0 mg,
0.18 mmol) were placed into a Schlenk flask equipped with a stir
bar under vacuum 5 min at room temperature. Benzene (20 mL)
was added and the mixture was stirred 1.5h. After filtration, the
benzene was reduced under vacuum until ~2 mL, and pentane was
added in order to induce the precipitation of an orange-yellow
solid, which was filtered, rinsed with pentane (5 ꢂ 5 mL), filtered
again and dried under vacuum in order to afford compound 16 in
67.5% (55.0 mg, 0.08 mmol), which melted at 242e245 ꢁC with
The synthesis was carried out as described for 13, using 8
(40.0 mg, 0.09 mmol) and 11. 2 L of Py-d5 (11.7 mg, 0.14 mmol) in
CD3CN (1.2 mL) and stirred for 1.5 h in a Vortex. However, two extra
independent additions of Py-d5 (3.7 L, 3.91 mg, 0.05 mmol) were
required, stirring in each case for ~ 2h. The solution was transferred
into a Schlenk tube, and after filtration, evaporation of CD3CN and
washing with pentane (2 ꢂ 5 mL), a yellow-orange solid was
m
m

J.I. de la Cruz-Cruz, M.A. Paz-Sandoval / Journal of Organometallic Chemistry 791 (2015) 107e118
117
decomposition. Compound 16 with 16Cl (16:16Cl, 10.5:1.0): 1H
Acknowledgments
NMR (500 MHz, CDCl3)
d
¼ 5.03 (d, J ¼ 17.0 Hz, H1), 5.07 (d,
J ¼ 10.2 Hz, H10), 7.51 (dt, J ¼ 17.0, 10.6 Hz, H2), 5.38 (t, J ¼ 11.1 Hz,
This work was financially supported by the National Council of
Science and Technology (Conacyt, 152280). J.I.C.C. is grateful for a
scholarship from Conacyt and Cinvestav. We thank Dr. Armando
H3), 6.17 (d, J ¼ 11.3 Hz, H4), 1.79 (s, C6Me6), 7.15e7.75 (m, PPh3). 31
P
{1H} NMR (202 MHz, CDCl3)
d
¼ 35.4 (s). 13C{1H} NMR (125 MHz,
ꢀ
CDCl3)
d
¼ 120.7 (C1), 133.1 (C2), 128.6 (C3), 138.3 (C4), 105.0 (s,
Ramirez-Monroy, Jose Rosas from BUAP and Marco Antonio Leyva
C6Me6), 15.7 (C6Me6), 134.0 (d, J ¼ 17.3 Hz, o, PPh3), 128.9 (d,
J ¼ 8.6 Hz, m, PPh3), 130.0 (s, p, PPh3). ESI þ TOF (C34H38O2N-
aPSClRuþ): m/z ¼ 701.0963; error 1.2304; DBE 15.5. IR(KBr):
3055(m), 2897(m,br), 2616(w,br), 2346(w), 2188(w,br), 1988(w,br),
1828(w,br), 1743(w), 1711(w), 1625(w), 1572(w), 1483(m), 1435(s),
1384(m), 1317(w), 1264(w), 1192(vs), 1091(s), 1051(vs,br), 914(m),
797(m), 753(s), 700(vs), 667(vs), 527(vs), 491(vs), 468(m), 425
(vw). Anal. Calcd for C34H38ClO2PRuS (678.23): C, 60.21; H, 5.65.
Found: C, 60.59; H, 5.28.
from Cinvestav for use and assistance with the crystal structure
determinations, and Patricia Juarez-Saavedra and M. Teresa Cortez-
Picasso for technical support in the chemical microanalysis, IR and
NMR experiments, respectively. The authors would also like to
thank Dr. Juan Olguín for valuable comments, Dr. Felipe Gonzalez-
ꢀ
ꢀ
Bravo and Daniel Morales Martinez, and Josue Israel Aleman Vega
for performing the electrochemical and DLS experiments,
respectively.
Appendix A. Supplementary data
4.15. Synthesis of [(HMB)Ru(Cl)(5-
and [(HMB)Ru(Cl)2(PHPh2)] (17Cl)
h-CH2CHCHCHSO2)(PHPh2)] (17)
Supplementary data related to this article can be found at http://
dx.doi.org/10.1016/j.jorganchem.2015.05.023.
Compound 7 (50.0 mg, 0.12 mmol) was placed into a Schlenk
flask equipped with a stir bar under vacuum 5 min at room
temperature. THF (10 mL) followed by 0.33 mL of PHPh2
(223.8 mg, 1.20 mmol, 10% w in hexane) were added; then the
mixture was stirred 1.5 h. After filtration of the golden solution,
the THF was reduced under vacuum until ~2 mL, and pentane was
added in order to induce the precipitation of an orange-yellow
solid, which was filtered, rinsed twice with 5 mL of pentane,
filtered again, recrystallized with CHCl3/pentane, and dried under
vacuum in order to afford compound 17 in 49.3% (35.5 mg,
0.06 mmol), which melts at 118e120 ꢁC, with decomposition.
Compound 17 with 17Cl (17:17Cl, 10.2:1.0): 1H NMR (500 MHz,
References
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C6D6)
d
¼ 4.98 (d, J ¼ 17.3 Hz, H1), 5.01 (d, J ¼ 9.9 Hz, H10), 8.21 (dt,
J ¼ 17.0, 11.0 Hz, H2), 5.72 (t, J ¼ 11.0 Hz, H3), 6.92 (d, J ¼ 11.3 Hz,
H4), 1.61 (s, C6Me6), 6.96e7.20 (m, PHPh2), 7.70e7.79 (m, PHPh2),
7.09 (d, J ¼ 422.8 Hz, PHPh2). 31P{1H} NMR (202 MHz, C6D6)
d
¼ 28.9 (s). 13C{1H} NMR (125 MHz, C6D6)
d
¼ 120.6 (C1), 133.6
~
[11] B.A. Paz-Michel, F.J. Gonzalez-Bravo, L.S. Hernandez-Munoz, I.A. Guzei,
(C2), 129.1 (C3), 138.9 (C4), 103.1 (s, C6Me6), 15.0 (C6Me6), 135.8 (d,
J ¼ 10.6 Hz, o, PHPh2), 133.0 (d, J ¼ 7.7 Hz, o, PHPh2), 130.5 (br,
J ¼ 1.9 Hz, m, PHPh2), 129.6 (br, J ¼ 1.9 Hz, m, PHPh2), 128.1 (s, p,
PHPh2), 128.0 (s, p, PHPh2). ESI þ TOF: m/z ¼ 603.082177, error:
-0.02575 ppm, DBE: 11.5. IR (KBr): 3052(m), 2920(m), 2347(w),
1966(w), 1821(w), 1626(m), 1571(m), 1480(m), 1437(s), 1384(m),
1312(w), 1178(vs), 1103(m), 1070(m), 1041(vs), 894(m), 859(m),
789(m), 743(s), 697(s), 663(vs), 539(m), 502(s), 477(m). Anal.
Calcd for C28H34ClO2PRuS,0.5CHCl3 (661.82): C, 51.72; H, 5.25; S,
4.84. Found: C, 51.62; H, 5.01; S, 4.62.
M.A. Paz-Sandoval, Organometallics 29 (2010) 3694e3708.
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doval, Organometallics 29 (2010) 3709e3721.
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361 (2008) 3094e3102.
ꢀ
~
[15] (a) B. A. Paz-Michel, Dissertation, Cinvestav, 2009;
(b) P. Juarez-Saavedra, M. A. Paz-Sandoval, unpublished results.
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X-ray diffraction measurements were made at 293(2) K (7) and
173(2) K (15) on an Enraf Nonius-Kappa CCD diffractometer, using
(b) Salts 2Li, 2LiMe, 2K and 2KMe should be used freshly prepared. They are
quite hygroscopic, even under nitrogen atmosphere showed after two weeks
to give non-selective reactions in the ruthenium chemistry with the conse-
quent low yields. The kinetic stability decreases in the following order: 2K >
2KMe > 2LiMe > 2Li.
graphite-monochromated Mo K
a
radiation (
l
¼ 0.71073 Å), and at
123(2) K (8) in a Agilent Nova Cu K
a
radiation (
l
¼ 1.54056 Å). The
structures were solved by direct methods, using SHELXS-2014
included in WinGX v.2014.1 and refined by a full-matrix least-
squares method based on F2 [32]. Absorption corrections were
performed by Multi-Scan. All non-hydrogen atoms were refined
with anisotropic thermal displacement coefficients unless specified
otherwise. The crystallographic information file (CIF) of com-
pounds 7(CCDC-1036731), 8(CCDC-1036729) and 15(CCDC-
1036730) contain the supplementary crystallographic data for this
paper. These data can be obtained free of charge from The Cam-
bridge Crystallographic Data Centre via www.ccdc.cam.ac.uk/data_
request/cif.
[22] P. Gamero-Melo, P.A. Melo-Trejo, M. Cervantes-Vasquez, N.P. Mendizabal-
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Sandoval, Organometallics 31 (2012) 170e190.
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118
J.I. de la Cruz-Cruz, M.A. Paz-Sandoval / Journal of Organometallic Chemistry 791 (2015) 107e118
I.R. Aleman-Figueroa, M.A. Paz-Sandoval, Inorg. Chim. Acta 359 (2006)
701e706.
[31] (a) The procedure in the preparation of [(p-cymene)Ru(
orange solid in similar yield than the previous reported. However, the purity
of this starting material is higher than the one obtained from the procedure
described in reference 31b, no matter which terpene was used. Recently, an
m
-Cl)Cl]2 is a modifi-
[31b]
cation of a previous reported synthesis.
Here the
a
-terpinene instead of
efficient and rapid microwave-assisted synthesis of [(p-cymene)Ru(m-Cl)Cl]2
a
-phellandrene have been used as starting material. After the reflux, the so-
has been reported in reference 31c;
(b) M.A. Bennett, T.-N. Huang, T.W. Matheson, A.K. Smith, Inorg. Synth. 21
lution is allowed to cool to room temperature, and cooled to ꢀ30 ꢁC over-
night. The precipitated red-brown solid was obtained by decantation and
washed with hexane until the washings are colorless. The microcrystalline
product was filtered off and dry under vacuum. The solid was extracted with
chloroform, filtered and evaporated under vacuum to afford, after drying, an
(1982) 74e78;
€
(c) J. Tonnemann, J. Risse, Z. Grote, R. Scopelliti, K. Severin, Eur. J. Inorg. Chem.
(2013) 4558e4562.
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