Isolation of ruthenium formyl complexes: Insight into the metal-mediated cleavage reaction of carbon-carbon triple bond

Article abstract of DOI:10.1016/j.jorganchem.2016.12.014

We describe a simple and efficient ruthenium-catalyzed reaction in which propargylic alcohol HC[tbnd]C[sbnd]C(Ph)₂OH is split into carbon monoxide CO, formaldehyde H₂C[dbnd]O and ketone (Ph)₂C[dbnd]O via cleavage of carbon-carbon triple and single bonds. A plausible reaction mechanism is proposed on the basis of ruthenium vinyl and formyl intermediates

Full text of DOI:10.1016/j.jorganchem.2016.12.014

Accepted Manuscript
Isolation of ruthenium formyl complexes: Insight into the metal-mediated cleavage
reaction of carbon-carbon triple bond
Yih-Hsing Lo, Ming-Che Li, Li-Yu Huang, Guan-Jie Hung
PII:
S0022-328X(16)30566-6
10.1016/j.jorganchem.2016.12.014
JOM 19737
DOI:
Reference:
To appear in: Journal of Organometallic Chemistry
Received Date: 5 August 2016
Revised Date: 19 November 2016
Accepted Date: 13 December 2016
Please cite this article as: Y.-H. Lo, M.-C. Li, L.-Y. Huang, G.-J. Hung, Isolation of ruthenium formyl
complexes: Insight into the metal-mediated cleavage reaction of carbon-carbon triple bond, Journal of
Organometallic Chemistry (2017), doi: 10.1016/j.jorganchem.2016.12.014.
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ACCEPTED MANUSCRIPT

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Isolation of Ruthenium Formyl Complexes: Insight into the Metal-
mediated Cleavage Reaction of Carbon-Carbon Triple Bond
Yih-Hsing Lo*, Ming-Che Li, Li-Yu Huang and Guan-Jie Hung
Department of Applied Physics and Chemistry, University of Taipei, Taipei 10048, Taiwan,
Republic of China. Corresponding author: E-Mail: yhlo@utaipei.edu.tw; Tel.: +886-2-2311-3040
Ext. 3111; Fax: +886-2-2389-7641
——————————————————————————————————————————
Abstract
We describe a simple and efficient ruthenium-catalyzed reaction in which propargylic alcohol
HC≡C-C(Ph) OH is split into carbon monoxide CO, formaldehyde H C=O and ketone (Ph) C=O
2
2
2
via cleavage of carbon-carbon triple and single bonds. A plausible reaction mechanism is
proposed on the basis of ruthenium vinyl and formyl intermediates.
Keywords: Tris(pyrazolyl)borato; Ruthenium; Propargylic alcohol; Vinyl; Formyl
——————————————————————————————————————————

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Introduction
Metal-catalyzed cleavage reactions of carbon-carbon bonds have been recognized as
fascinating topics in organic reaction [1]. Recently, various unusual and helpful catalytic
processes involving C-C and C=C bonds cleavage have been investigated [2]. What has
remained unexplored is the cleavage of C≡C bond, which is a difficult target in organic
chemistry [3]. Most previous studies on cleavage of C≡C bond have focused on stoichiometric
organometallic reactions, such as alkyne-ligand scission on metal complexes [4], water-assisted
splitting of alkyne into alkane and coordinated CO [5], as well as oxidative cleavage of alkynes
to carboxylic acids [6]. Except for metathesis of alkynes, there have been very few reported
examples for the metal-catalyzed organic alkyne cleavage reactions [7-13]. Because of the
importance of carbon-carbon bond cleavage, we explored to identify a new pathway for the
cleavage of alkyne. Recently, we report the novel one-step synthesis of alkenyl ketone
complexes from TpPPh (HN=CPh )RuCl (1, Tp = HB(pz) , pz = pyrazolyl) by incorporation of
3
2
3
two H-C≡C-Ph and one H O molecule, through combination of insertion and hydration process
2
[14]. Following a preliminary account of this work, we now disclose the results of detailed
catalytic and structural investigations on the reaction of H-C≡C-CPh OH with 1. This reaction is
2
mechanistically interesting because the mechanism is proposed to involve cleavage of C≡C and
C-C bonds via ruthenium vinyl and formyl intermediates.
Results and Discussion
We first examined the effect of solvents and catalysts on catalytic reaction. Treatment of the
1
,1-diphenylpropargyl alcohol with 1 (5.0 mol %) in MeOH at room temperature for 4 h gave
benzophenone (2) in 83% yield (Scheme 1). Intriguingly, a small sharp peak of free

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1
formaldehyde at δ 9.61 was observable in H NMR spectrum. GC-analysis of gaseous mixture of
the reaction solution in a sealed tube showed the presence of carbon monoxide and formaldehyde.
Ketone 2 was obtained in 25% yield in the absence of water. Under similar conditions, other
solvents were less effective than methanol and gave 0-26% yields of 2. MeCN showed a low
3 3 2
activity to give 26% yield of 2. The cationic complex [TpPPh (CH CN) Ru]Cl [15] could be
isolated. In solvent with weaker coordinative ability, such as acetone or tetrahydrofuran (THF),
the reaction also afforded 2 (12% yield), but the ruthenium portion decomposed. In chlorinated
solvents, such as CH Cl or CHCl , the reaction afforded a large amount of OPPh . No reaction
2
2
3
3
was observed in H O, even under drastic, vigorous condition. Under the same conditions,
2
Tp(PPh ) RuCl [16] and other catalysts including TpPPh (MeCN)RuCl [15] and
3
2
3
TpPPh (PhCN)RuCl [17] failed to give significant amounts of 2 but rather gave uncharacterized
3
black tar.
Scheme 1 Reaction of the 1,1-diphenylpropargyl alcohol with 1 (5.0 mol %) in MeOH
C3
C9
C6
B1
N6
C8
N4
C12
N2
C2
C5
N3
C7
C11
C13
N1
C3
N5
C4
C14
C10
Ru1
C30
H28
P1
C15
C23
C24
C22
O1
C28
C29
C17
C16
C27
C25
H29a H29b
C18
C26
C21
C19
C20
Fig. 1 The ORTEP drawing of 3 showing thermal ellipsoids at the 50% probability level. All hydrogen atoms, except H(28),
H(29a) and H(29b), are omitted for clarity. Selected bond lengths (Å) and angles (°): Ru(1)-N(1) 2.190(4), Ru(1)-N(3) 2.120(3),
Ru(1)-N(5) 2.167(3), Ru(1)-C(28) 2.009(5), Ru(1)-C(30) 1.868(6), (28)-C(29) 1.148(6), C(30)-O(1) 1.069(5); Ru(1)-C(30)-O(1)
1
72.1(6), Ru(1)-C(28)-C(29) 142.6(5).

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However, in the course of reaction no intermediate could be detected by NMR spectroscopy,
but only the reaction product 2. Fortunately, complex 1 was allowed to react with propargyl
0
alcohol in methanol at 0 C for 4h, isolated the ruthenium vinyl complex Tp(OC)(PPh )Ru-
3
C(H)=CH (3) (78% yield) and the ruthenium formyl complex Tp(OC)(PPh )Ru-C(O)H (4) (6%
2
3
yield) after silica gel column separation using a CH Cl eluent. When the reaction proceeded
2
2
using 10 equiv of H O, the yield of 3 was increased (86% yield) in contrast to that of 4 (3%
2
yield). The spectroscopic data were sufficient to unequivocally assign the structure of 3. The IR
-l
spectrum of 3 in KBr contains very strong bands at 1951 cm and a medium intensity absorption
-
l
at 1587 cm , which are assigned to ν(C≡O) and ν(C=C), respectively. With the help of 2D-NMR
1
experiments, the signals of the three protons of the vinyl group are located in the H NMR
3
1
1
spectrum as two multiplets at δ 5.20-5.27 and 5.83-5.86. The P{ H} NMR spectrum displays a
singlet at δ 50.6. An ORTEP view of complex 3 is shown in Figure 1. The coordination
3
geometry around ruthenium in 3 can be viewed as a distorted octahedron with Tp, PPh , carbonyl
◦
(
CO) and vinyl (HC=CH ) ligands. The C(29)–C(28)–Ru(1) angle, 142.6(5) , is surprisingly
2
2
large for an sp -hybridized C atom
The complex 4 has been characterized by spectroscopic and elemental analysis. The IR
-l
-l
spectrum contains two strong bands at 1952 cm and 1609 cm , corresponding to the
1
3
1
characteristic stretching frequency of C≡O and C=O groups, respectively. In the C{ H} NMR
spectrum, a strongly deshielded resonance as a doublet at δ 263.7 with JPC = 16.3 Hz is assigned
to formyl group and a doublet at δ 206.3 with JCp = 15.3 Hz is assigned to carbonyl group. The
1
H NMR spectrum shows a broad resonance centered at δ 9.61 assignable to C(O)H group. The
3
1
1
P{ H} NMR spectrum displays a singlet resonance at δ 41.8. The X-ray analysis of the single
crystals of 4 (Fig. 2) revealed the molecular structure of the complex with cis-orientation of the

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Ru-CO and Ru-C(O)H moieties. Stable formyl complexes have been described for several group
VIII and group IX late transition metals [18]. Hydride nucleophilic addition on coordinated
carbon monoxide can lead to transition-metal formyl complexes [19], which have been proposed
as intermediates in the Fischer-Tropsch reaction [20]. To the best of our knowledge, this is the
first example that the ruthenium complex with alkynol yields a thermally stable and pure formyl
product.
C9
C3
B1
C6
N4
N3
N12
C5
C2
N6
N5
C8
C12
C4
N11
C1
C7
C13
C11
Ru1
C10
H29
C28
C14
P1
C29
C16
C15
O2
O1
C21
C17
C27
C18
C22
C23
C26
C19
C20
C24
C25
Fig. 2 The ORTEP drawing of 4 showing thermal ellipsoids at the 50% probability level. All hydrogen atoms, except C(28)–H,
are omitted for clarity. Selected bond lengths (Å) and angles (°): Ru(1)-N(1) 2.127(6), Ru(1)-N(3) 2.190(7), Ru(1)-N(5) 2.175(7),
Ru(1)-C(28) 1.877(11), Ru(1)-C(29) 2.005(10), (29)-O(2) 1.230(14), C(28)-O(1) 1.083(12); O(1)-C(28)-Ru(1) 171.9(10), O(2)-
C(29)-Ru(1) 140.8(10).
Interestingly, isolated complex 3 in methanol for 2 h gave rise to 4 and benzylphenone. To
18
find the source of the oxygen atom, we carried out the reaction by adding H O into a carefully
2
dehydrated solvent in air. The mass spectrum of Tp(OC)(PPh )Ru-C(O)H, thus obtained,
3
18
displayed the parent peak at m/z = 634.1, indicating no incorporation of O. The oxygen atom
was not from CH OH in the reaction because the reaction of 3 in dehydrated CH Cl under
3
2
2

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nitrogen also gave formyl product 4. Thus, the oxygen atom in formyl product was confirmed to
come from oxygen in air, not from water or MeOH. Bubbling oxygen into the reaction could
appreciably enhance the reaction rate. Therefore, along with the fact that a small amount of
OPPh was isolated from the reaction, dissociation of the phosphine ligand is considered to be a
3
key step, possibly creating a vacant site for the coordination of an oxygen molecule. The reaction
of 3 with oxygen in the presence of radical trap 2,2,6,6 tetramethylpiperidine-1-oxyl (TEMPO)
and in MeOH in air nevertheless afforded 4; this experiment suggested that the reaction does not
proceed through a radical process.
R
R
H
H
R
R
-
H O
OH
Cl-
2
Cl-
R
L L [Ru] Cl
L1L2[Ru]
C
L1L2[Ru]
C
C
C
1
2
MeOH
OH
R
B
I
A
H O
2
[
Ru] = TpRu, L = Ph C=NH, L = PPh , R = Ph
1
2
2
3
HCl
R
L2
O2
O
OC
OC
-L1
[
Ru]
[Ru]
L2[Ru]
OC
L L [Ru]
1 2
O
O
O
R
O
R
R
R
R
R
D'
R
3
C
D
L2
O
O
CO
H
H
L1, HCl
Ph
Ph
L2[Ru]
OC
H
L L [Ru] Cl
1 2
O
1
4
Scheme 2 A plausible reaction mechanism is proposed on the basis of ruthenium vinyl and formyl intermediates.
We propose a plausible mechanism (Scheme 2) that involves the formation of cationic
ruthenium allenylidene species B via dehydration of the γ-OH group of cationic ruthenium
2
4
vinylidene complex A. Subsequent nucleophilic attack of a water molecule onto its α-carbon
gives ruthenium-acyl species C derived from the elimination of HCl, followed by formation of 3

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fron decarbonylation of species C. The oxygenation may proceed initially through dissociation
of PPh , providing a vacant site. Then O is activated, possibly either by an end-on coordination
3
2
to the metal center to form D or by a side-on coordition mode generating D’ [21]. Nevertheless,
D’ may be a more stable form [22], so that D is more reactive. Thereafter, coupling of oxo and
vinyl ligands, assisted by incoming PPh , could yield 4 and benzophenone. Finally, reductive
3
elimination regenerated active ruthenium catalyst 1 in addition to ketone and carbon monoxide.
The preceding proposed mechanism involves cleavage of the carbon-carbon triple and single
bonds of the propargylic alcohol. This reaction process is in sharp contrast to the ruthenium
catalyzed transformation of ethynyl alcohol into alkene and carbon monoxide [12].
Concluding Remarks. In summary, we report the new ruthenium-catalyzed transformation of
1
,1-diphenylpropargyl alcohol into benzylphenone, carbon monoxide and formaldehyde. A
plausible mechanism is proposed on the basis of ruthenium vinyl and formyl intermediates. The
development of new catalytic processes based on this principle is under investigation.
Experimental Procedures
General Procedure. All manipulations were performed under nitrogen using vacuum-line,
drybox, and standard Schlenk techniques. CH CN and CH Cl were distilled from CaH and
3
2
2
2
diethyl ether and THF from Na/ketyl. All other solvents and reagents were of reagents grade and
were used without further purification. NMR spectra were recorded on a Bruker AC-300
1
31
11
13
instrument at 300 MHz ( H), 121.5 MHz ( P), 267.45 MHz ( B) or 75.4 MHz ( C) using
SiMe , BF •Et O or 85% H PO as standard or on an Avance 500 FT-NMR spectrometer. FAB
4
3
2
3
4
mass spectra were recorded on a JEOL SX-102A spectrometer. Elemental analyses and X-ray
diffraction studies were carried out at the Regional Center of Analytical Instrument at National
Taiwan Normal University.

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Procedure for Catalytic Reactions. In a 25 mL Schlenk tube equipped with a Teflon stopcock,
the ruthenium catalyst Tp(PPh )(NH=CPh )Ru-Cl (1, 5 mol %) in 1 mL of methanol. Excess 1,1-
3
2
diphenylpropargyl alcohol (0.80 mmol) was added to the solution, and the reaction mixture was
stirred at room temperature for 4 h. Then the solution was evaporated under high vacuum. The
residue was extracted with Et O, and the Et O solution was chromatographed on silica gel (n-
2
2
hexane/Et O) in air. The rotary evaporation led to the ketone products.
2
2
Reaction of complex 1 with HC≡CCPh OH. To a distilled methanol (20 mL) solution of 1
(1.00 g, 1.3 mmol) was added propargyl alcohol (1 mL, 16.8 mmol) at room temperature. The
0
reaction mixture was stirred at C for 4 h. Then the resulting solution was dried in vacuo. The
residue was extracted with hexane and the residual solid was further washed with diethyl ether to
give the complex {Tp(PPh
concentrated and was then eluted with CH
Tp(PPh )(OC)Ru-(HC=O)} (4) (0.005 g, 6% yield). Spectroscopic data for 3: IR (KBr, cm ):
ν(B-H) 2451 (br), ν(C≡O) 1951 (vs), ν(C=C) 1587 (w). H NMR (CDCl ): δ 7.86 (d, J = 2.0
3
)(OC)Ru-(HC=CH
2
)} (3) (0.6 g, 78% yield). The hexane extract was
2
Cl on a silica gel packed column to give
2
-1
{
3
1
3
H-H
Hz, 1H, Tp), 7.74 (d, JH-H = 2.0 Hz, 1H, Tp), 7.61 (d, JH-H = 2.1 Hz, 1H, Tp), 7.53 (d, JH-H = 2.1
Hz, 1H, Tp), 7.24-6.90 (m, Tp, Ph), 6.31 (d, JH-H = 1.9 Hz, 1H, Tp), 6.11 (t, JH-H = 2.0 Hz, 1H,
13
Tp), 6.03 (t, JH-H = 2.0 Hz, 1H, Tp), 5.20-5.27, 5.83-5.86 (mx2, 3 H, CH=CH
2
). C NMR
(
(
CDCl ): δ 206.6 (d, J = 15.9 Hz, CO), 153.1 (br, HC=), 144.3 - 111.5 (m, Tp, PPh ), 107.1
3
P–C
3
31
+
+
+
2 3 2
=CH ). P NMR (CDCl ): δ 50.6. MS (FAB) m/z: 632.1 (M ), 605.1 (M , HC=CH ), 577.1 (M ,
HC=CH , CO). Anal. Calcd for C H BN OPRu (632.12): C, 57.06; H, 4.47; N, 13.31. Found:
2
30 28
6
C, 57.01; H, 4.39; N, 13.12.
-1
Spectroscopic data for 4: IR (KBr, cm ): ν(B-H) 2449 (br), ν(C≡O) 1952 (vs), ν(C=O) 1609 (vs).
1
H NMR (CDCl ): δ 9.81 (br, 1H, C(O)H), 7.81 (d, JH-H = 1.9 Hz, 1H, Tp), 7.61 (d, JH-H = 2.0 Hz,
3

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1
6
1
H, Tp), 7.52 (d, JH-H = 1.9 Hz, 1H, Tp), 7.41 -7.10 (m, Ph, Tp), 6.85 (1H, Tp), 6.71 (1H, Tp),
.61 (1H, Tp), 6.42 (t, JH-H = 2.1 Hz, 1H, Tp), 5.92 (t, JH-H =2.1 Hz, 1H, Tp), 5.82 (t, JH-H =2.1 Hz,
1
3
H, Tp). C NMR (CDCl ): δ 263.7 (d, J = 16.3 Hz, Ru-C(O)H), 206.3 (d, JP-C = 15.3 Hz, Ru-
3
P-C
3
1
+
CO), 146.9 -105.6 (m, Ph, PPh
3
, Tp). P NMR (CDCl
3
): δ 41.8. MS (FAB) m/z:634.1 (M ),
+
+
6
05.1 (M , HCO), 577.1 (M , HCO, PPh ). Anal. Calcd for C H B N O PRu: C, 54.99; H, 4.14;
3
29 26
6
2
N, 13.27. Found: C, 54.81; H, 4.09; N, 13.08.
Structure Determination of Complexes 3 and 4. Single crystal X-ray diffraction data were
measured on a Bruker SMART Apex CCD diffractometer using µ(Mo Kα) radiation ( = 0.71073
λ
Å). The data collection was executed using the SMART program; cell refinement and data
reduction were performed with the SAINT program. The structure was determined using the
SHELXTL/PC program and refined using full-matrix least-squares [23]. Crystallographic
refinement parameters [24] of complexes 3 and 4 selected bond distances and angles are listed in
the Supporting Information.
Acknowledgment. We gratefully acknowledge the financial support in part from the Ministry of
Science and Technology, Taiwan (MOST 104-2113-M-845-001). We also thank Mr. Ting Shen
Kuo (Department of Chemistry, National Taiwan Normal University, Taiwan) for his assistance
in X-ray single crystal structure analysis
Supporting Information Available: Complete crystallographic data for 3 and 4 (CIF).
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2
575.
[
[
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2
2
2
1/2
[
24] GOF = [Σ[w(F o - F c) ]/(n - p)] , where n and p denote the number of data and parameters.
2
o
2
2 2 1/2
2
2
R1= (Σ||F | - |F ||)/Σ|F |, wR2 = [Σ- [w(F - F ) ]/å[w(Fo ) ]] where w = 1/[σ (F ) +
o
c
o
c
2
o
2
2
2
(
aP) + bP] and P = [(max; 0, F ) + 2Fc ]/3.
o

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ꢀ
W disclose the results of detailed catalytic and structural investigations on the
2 3 2
reaction of H-C≡C-CH OH with TpPPh (HN=CPh )RuCl.
ꢀ
ꢀ
A number of new ruthenium complexes have been prepared.
A plausible reaction mechanism is proposed on the basis of ruthenium vinyl and
formyl intermediates.
ꢀ
Their structures are elucidated by IR, NMR and X-ray crystallography.