RutheniumII(p-cymene) complexes bearing ligands of the type 1-[2′-(methoxycarbonyl)phenyl]-3-[4′-X-phenyl]triazenide (X?=?F, Cl, Br, I): Synthesis, structure and catalytic activity

Article abstract of DOI:10.1016/j.ica.2017.06.064

The synthesis and characterization of triazenes of the type 1-[2′-(methoxycarbonyl)phenyl]-3-[4′-X-phenyl]triazene [X?=?F (1), Cl (2), Br (3), I (4)] as precursors of triazenide ligands for the preparation of their complexes of formula [Ru{1-(2′-methoxyca

Full text of DOI:10.1016/j.ica.2017.06.064

Accepted Manuscript
RutheniumII(p-cymene) complexes bearing ligands of the type 1-[2'-(methoxy-
carbonyl)phenyl]-3-[4'-X-phenyl]triazenide (X= F, Cl, Br, I): synthesis, struc-
ture and catalytic activity
Erick Correa-Ayala, Carlos Campos-Alvarado, Daniel Chávez, David Morales-
Morales, Simón Hernández-Ortega, Juventino J. García, Marcos Flores-Álamo,
Valentín Miranda-Soto, Miguel Parra-Hake
PII:
S0020-1693(17)30673-4
http://dx.doi.org/10.1016/j.ica.2017.06.064
ICA 17713
DOI:
Reference:
Inorganica Chimica Acta
To appear in:
Received Date:
Revised Date:
Accepted Date:
4 May 2017
23 June 2017
28 June 2017
Please cite this article as: E. Correa-Ayala, C. Campos-Alvarado, D. Chávez, D. Morales-Morales, S. Hernández-
Ortega, J.J. García, M. Flores-Álamo, V. Miranda-Soto, M. Parra-Hake, RutheniumII(p-cymene) complexes bearing
ligands of the type 1-[2'-(methoxycarbonyl)phenyl]-3-[4'-X-phenyl]triazenide (X= F, Cl, Br, I): synthesis, structure
and catalytic activity, Inorganica Chimica Acta (2017), doi: http://dx.doi.org/10.1016/j.ica.2017.06.064
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RutheniumII(p-cymene) complexes bearing ligands of the type
1-[2'-(methoxycarbonyl)phenyl]-3-[4'-X-phenyl]triazenide (X= F, Cl, Br, I):
synthesis, structure and catalytic activity
Erick Correa-Ayalaa, Carlos Campos-Alvaradoa, Daniel Cháveza, David Morales-Moralesb,
Simón Hernández-Ortegab, Juventino J. Garcíac, Marcos Flores-Álamoc, Valentín Miranda-
Sotoa,*, Miguel Parra-Hakea,*
a Centro de Graduados e Investigación, Instituto Tecnológico de Tijuana, Apartado Postal 1166, Tijuana, B.C. 22000, México
bInstituto de Química, Universidad Nacional Autónoma de México, Circuito Exterior.Cd. Universitaria Coyoacán, México D.F.
04510, México
cFacultad de Química, Universidad Nacional Autónoma de México, Circuito Exterior Cd. Universitaria Coyoacán, México D.F.
04510, México
Abstract
The synthesis and characterization of triazenes of the type 1-[2'-
(methoxycarbonyl)phenyl]-3-[4'-X-phenyl]triazene [X = F (1), Cl (2), Br (3), I (4)] as
precursors of triazenide ligands for the preparation of their complexes of formula [Ru{1-(2'-
methoxycarbonylphenyl)-3-(4'-X-phenyl)triazenide}(Cl)(p-cymene)] [X = F (6), Cl (7), Br (8), I
(9), CH3 (10)] are reported. Molecular structures for all four triazenes (1-4), and of complexes 6,
9 and 10 were determined by X-ray diffraction studies. Complexes 6-10 were tested as catalysts
in the transfer hydrogenation of acetophenone in the presence and in the absence of base. The
best results were obtained in the presence of base with yields in the range of 86-94%, whereas
even in the absence of base yields in the range 42-65% were achieved.
1. Introduction
There has been considerable attention on the coordination chemistry of 1,3-
bis(aryl)triazenide ligands primarily because of their varied modes of binding [1,2]. These
ligands can act as monodentate binding through a terminal [3,4] or central nitrogen [5,6], as
bidentate to form a chelate [7,8], bidentate bridging two metal centers [9,10] or tricoordinate
and tetracoordinate bridges [11,12] (Fig. 1).
1

Figure 1. The coordination modes of the 1,3-bis(aryl)triazenide ligands.
Another reason for the current interest in 1,3-bis(aryl)triazenide ligands is their wide
range of derivatives available through the addition of different substituents on the aryl group. In
this direction, our research group has found that the incorporation of donor groups at the ortho
position of the 1,3-bis(aryl)triazenide ligands can modify the coordination chemistry of the
ligand [13-17] and the reactivity of their respective complexes [16,17], which in turn determine
their catalytic activity.
Ru(p-cymene) complexes bearing 1,3-bis(aryl)triazenide ligands are attracting
considerable interest from the point of view of their synthesis, structure, and catalytic and
biological activity. Thus, Strähle and coworkers reported the synthesis and structure of the first
complex of this type, [RuCl(η2-1,3-ClC6H4NNNC6H4Cl)(η6-p-cymene)] [18]. Albertin and
coworkers, reported neutral complexes [RuCl(η2-1,3-ArNNNAr)(η6-p-cymene)], their structures
and catalytic activity on hydrogenation of 2-cyclohexen-1-one and cynnamaldehyde under H2
pressure [19]. Košmrlj, Osmak and coworkers have reported
a
series of 1,3-
bis(aryl)triazenido(p-cymene)ruthenium(II) complexes with a high in vitro anticancer activity as
the first study on the biological properties of this class of complexes [20].
As part of our ongoing research, we have recently reported a series of half-sandwich
Ru(p-cymene) derivatives with symmetrically and unsymmetrically ortho-substituted 1,3-
bis(aryl)triazenide ligands (Fig. 2), which proved to be catalytically active in the transfer
hydrogenation of ketones in the absence or in the presence of base [21]. Furthermore, we found
that the nature of the functional group at the ortho position of the 1,3-bis(aryl)triazenide ligands
2

Figure 2. Ruthenium complexes previously reported [21].
can be tuned in order to modulate the catalytic properties of their complexes. The most
promising result was the ability of complex A to catalyze the transfer hydrogenation of
acetophenone under base-free conditions, since most pre-catalysts require a base to form the
hydride complex as the active catalyst. Thus, reports in this area are rather scarce [22-25] and in
most cases the precursors are hydride complexes [26-30] or an additive is required [31-33].
Based on those results, we turned our attention to analogues of complex A in which one of the
ortho-methoxycarbonyl aryl groups was replaced by a halogen para-substituted aryl group with
the aim of testing their catalytic activity. We hypothesized that these new complexes would be
active catalysts in the transfer hydrogenation of ketones. It was expected that the relative
catalytic efficiency to be dependent on the para-substituent.
Here we report on the synthesis of four new triazenes of the type 1-[2'-
(methoxycarbonyl)phenyl]-3-[4'-X-phenyl]triazene (X = F, Cl, Br, I) as the triazenide ligand
precursors, their rutheniumII(p-cymene) complexes and results on the evaluation of these
complexes as catalysts in the transfer hydrogenation of acetophenone, particularly under base
free conditions.
3

2. Experimental Section
2.1. General comments
All synthetic work was carried out in air or under argon using standard Schlenk
techniques or an inert atmosphere dry-box, where indicated. All solvents were dried over
appropriate drying agents. RuCl3•3H2O (Aldrich) and other reagents are commercially available
and were used as received. [RuCl2(p-cymene)]2 [34] and {1-[2'-(methoxycarbonyl)phenyl]-3-
[4'-(methyl)phenyl]}triazene (5) [15], were synthesized according to previously reported
procedures. NMR spectra were recorded at 400 MHz with a Bruker Avance III spectrometer at
1
30 °C unless otherwise specified. H and 13C NMR chemical shifts are reported in ppm
referenced to residual solvent resonances (1H NMR: 7.16 for C6HD5 in C6D6, 1.94 for CHD2CN
in CD3CN, 2.05 for acetone-d5 in acetone-d6. 13C NMR: 128.39, 1.39, and 29.92 for benzene-d6,
acetonitrile-d3 and acetone-d6, respectively). Coupling constants J are given in Hertz (Hz). IR
spectra were recorded on a Perkin-Elmer FT-IR 1605 spectrophotometer. Melting points were
measured in an Electrothermal GAC 88629 apparatus. Mass spectra were obtained by direct
insertion on a Agilent Technologies 59756 Instrument. High Resolution Mass Spectrometry
(HRMS) data were obtained in a micrOTOF-Q III MS instrument with electrospray ionization
using sodium formate as calibrant.
2.2. Ligands
2.2.1. 1-[2'-(methoxycarbonyl)phenyl]-3-[4'-(fluoro)phenyl]triazene (1)
Methyl anthranilate (2.0 mL, 15.6 mmol) dissolved in water (5 mL) was mixed with
37% HCl (4.6 mL, 46.8 mmol) at 0 ºC, whereupon an aqueous solution (15%) of sodium nitrite
(1.3 g, 18.7 mmol) was added dropwise with stirring. Once the amine was dissolved, a 15%
solution of 4-(fluoro)aniline (1.7 g, 15.6 mmol) in methanol (11 mL) was added at 0 ºC, and the
resulting solution stirred for 1 h. Then the reaction mixture was neutralized with a 15% aqueous
solution of NaOAc (25 mL) to give a yellow precipitate. The product was purified by
4

crystallization at ̶ 5 ºC from a 9:1 ethyl acetate/hexane mixture to obtain a yellow crystalline
solid (3.6 g, 13.4 mmol, 86%). MP = 109-112 ºC. IR(ATR): 3257, 3023, 2945, 1685, 1584,
1
1495, 1462, 1265, 1172, 1133, 1083, 837, 749 cm–1. H NMR [CDCl3, 400 MHz]: δ 12.41 (s,
1H, NH), 8.01 (dd, J = 8.0, 1.6 Hz, 1H, ArA3), 7.90 (dd, J = 8.4, 0.8 Hz, 1H, ArA6), 7.59 (dd, J =
9.2, 5.2 Hz, 2H, ArB2,6), 7.50 (td, J = 7.6, 1.6 Hz, 1H, ArA5), 7.10 (t, J = 9.2 Hz, 2H, ArB3,5), 7.01
(td, J = 7.4, 1.2 Hz, 1H, ArA4), 3.94 (s, 3H, OCH3(A8)). 13C{1H} NMR [CDCl3, 100 MHz]: δ
168.6 (CA7), 163.2 (d, JCF = 244 Hz, CB4), 147.1 (d, JCF = 3 Hz, CB1), 144.6 (CA1), 135.6 (CA5),
131.9 (CA3), 124.2 (d, JCF = 9 Hz, CB2,6), 122.3 (CA4), 116.7 (d, JCF = 23 Hz, CB3,5), 115.2 (CA6),
112.8 (CA2), 52.7 (CA8). MS-EI m/z (%): 273 (9) [M]+, 245 (33) [M – N2]+, 123 (73) [M –
NH(C6H4)COOCH3]+, 95 (100) [M – N3H(C6H4)COOCH3]+. HRMS (ESI-TOF) m/z: [M+Na]+
Calcd for C14H12FN3O2Na 296.0806; Found 296.0806.
2.2.2. 1-[2'-(methoxycarbonyl)phenyl]-3-[4'-(chloro)phenyl]triazene (2)
Ligand 2 was prepared in the same manner as triazene 1, using 4-(chloro)aniline (2.0 g,
15.6 mmol) to obtain a yellow crystalline solid (3.3 g, 11.3 mmol, 72%). MP = 113-115 ºC.
1
IR(ATR): 3243, 3023, 2938, 1685, 1583, 1500, 1455, 1263, 1158, 1086, 832, 752 cm–1. H
NMR [CDCl3, 400 MHz]: δ 12.41 (s, 1H, NH), 8.02 (dd, J = 8.0, 1.6 Hz, 1H, ArA3), 7.88 (dd, J
= 8.4, 0.8 Hz, 1H, ArA6), 7.53 (d, J = 8.8 Hz, 2H, ArB2,6), 7.50 (td, J = 7.6, 1.6 Hz, 1H, ArA5),
7.35 (d, J = 8.8 Hz, 2H, ArB3,5), 7.03 (t, J = 7.6, 0.8 Hz, 1H, ArA4), 3.93 (s, 3H, OCH3(A8)).
13C{1H} NMR [CDCl3, 100 MHz]: δ 167.7 (CA7), 148.3 (CB1), 143.8 (CA1), 134.6 (CA5), 133.4
(CB4), 131.3 (CA3), 129.3 (CB3), 123.0 (CB2), 121.4 (CA4), 114.7 (CA6), 112.2 (CA2), 52.3 (CA8).
EI-MS m/z (%): 291 (2) [M + 2]+, 289 (13) [M]+, 139 (81) [M – NH(C6H4)COOCH3]+, 111
(100) [M –N3H(C6H4)COOCH3]+. HRMS (ESI-TOF) m/z: [M
+
Na]+ Calcd for
5

C14H12ClN3O2Na 312.0510; Found 312.0495. Anal. Calc. for C14H12ClN3O2 (289.06): C, 58.04;
H, 4.18; N, 14.50%. Found: C, 57.76; H, 4.01; N, 14.63%.
2.2.3. 1-[2'-(methoxycarbonyl)phenyl]-3-[4'-(bromo)phenyl]triazene (3)
Ligand 3 was prepared in the same manner as triazene 1, using 4-(bromo)aniline (2.7 g,
15.6 mmol) to obtain a yellow crystalline solid (9.2 g, 27.5 mmol, 71%). MP = 108-110 ºC.
1
IR(ATR): 3255, 3071, 2945, 1685, 1581, 1500, 1455, 1261, 1153, 1004, 834, 753 cm–1. H
NMR [CDCl3, 400 MHz]: δ 12.42 (s, 1H, NH), 8.00 (dd, J = 8.0, 1.6 Hz, 1H, ArA3), 7.89 (dd, J
= 8.4, 0.8 Hz, 1H, ArA6), 7.53 (t, 1H, ArA5), 7.52 (d, J = 8.8 Hz, 2H, ArB3,5), 7.48 (d, J = 8.8 Hz,
2H, ArB2,6), 7.03 (td, J = 7.6, 1.2 Hz, 1H, ArA4), 3.93 (s, 3H, OCH3(A8)). 13C{1H} NMR [CDCl3,
100 MHz]: δ 167.8 (CA7), 148.5 (CB1), 143.8 (CA1), 134.6 (CA5), 132.3 (CB2,6), 131.3 (CA3),
123.3 (CB3,5), 121.54 (CA4), 121.52 (CA4), 114.7 (CA6), 112.2 (CA2), 52.3 (CA8). EI-MS m/z (%):
335 (6) [M + 2]+, 333 (6) [M]+, 305 (1) [M – N2] +, 183 (62) [M – NH(C6H4)COOCH3]+, 155
(100) [M – N3H(C6H4)COOCH3]+.
2.2.4. 1-[2'-(methoxycarbonyl)phenyl]-3-[4'-(iodo)phenyl]triazene (4)
Ligand 4 was prepared in the same manner as triazene 1, using 4-(iodo)aniline (3.4 g,
15.6 mmol) to obtain a yellow crystalline solid (4.16 g, 10.92 mmol, 70%). MP = 126-128 ºC.
1
IR(ATR): 3253, 3062, 2945, 1685, 1580, 1497, 1454, 1258, 1152, 1004, 832, 753 cm–1. H
NMR [CDCl3, 400 MHz]: δ 12.42 (s, 1H, NH), 8.02 (dd, J = 8.0, 1.6 Hz, 1H, ArA3), 7.89 (d, J =
8.4 Hz, 1H, ArA6), 7.72 (d, J = 8.4 Hz, 2H, ArB3,5), 7.52 (td, J = 8.0, 1.4 Hz, 1H, ArA5), 7.35 (d,
J = 8.4 Hz, 2H, ArB2,6), 7.03 (t, J = 8.0 Hz, 1H, ArA4), 3.93 (s, 3H, OCH3(A8)). 13C{1H} NMR
[CDCl3, 100 MHz]: δ 167.7 (CA7), 149.4 (CB1), 143.8 (CA1), 138.3 (CB2,6), 134.6 (CA5), 131.3
(CA3), 123.6 (CB3,5), 121.5 (CA4), 114.7 (CA6), 112.3 (CA2), 93.0 (CB4), 52.1 (CA8). EI-MS m/z
(%): 381 (9) [M]+, 353 (4) [M – N2] +, 231 (84) [M – NH(C6H4)COOCH3]+, 203 (100) [M –
N3H(C6H4)COOCH3]+. HRMS (ESI-TOF) m/z: [M + Na]+ Calcd for C14H12IN3O2Na 403.9866;
Found 403.9865.
6

2.3. Synthesis of complexes
2.3.1. [Ru{1-(2'-methoxycarbonylphenyl)-3-(4'-fluorophenyl)triazenide}(Cl)(p-cymene)] (6)
1-[2'-(methoxycarbonyl)phenyl]-3-[4'-fluorophenyl]triazene (1) (44.6 mg, 0.1633 mmol, 2.0 eq)
was dissolved in CH2Cl2 (5 mL) and triethylamine (33.0 mg, 0.3266 mmol, 4.0 eq) was added
with stirring. Then, a solution of [RuCl2(p-cymene)]2 (50.0 mg, 0.0816 mmol, 1.0 eq) in CH2Cl2
(5 mL) was slowly added and the mixture stirred for 24 h at room temperature. A dark yellow
solution was formed, which was filtered through an alumina column. The solvent was removed
under reduced pressure to obtain a yellow solid. Recrystallization by vapor diffusion of hexane
into a concentrated solution of the product in THF at room temperature gave yellow crystals,
suitable for X-ray diffraction analysis (64.0 mg, 0.1178 mmol, 72%). MP =108-110 ºC.
1
IR(ATR): 3063, 2971, 1716, 1598, 1498, 1449, 1262, 1225, 1212, 1090, 837, 753 cm–1. H
NMR [(CD3)2CO, 400 MHz]: δ 7.45 (td, J = 7.2, 1.6 Hz, 1H, ArA5), 7.39 (dd, J = 7.6, 1.2 Hz,
1H, ArA3), 7.27 (dd, J = 9.2, 4.8 Hz, 2H, ArB2,6), 7.24 (dd, J = 7.2, 0.8 Hz, 1H, ArA6), 7.14 (td, J
= 7.6, 1.2 Hz, 1H, ArA4), 7.06 (t, J = 8.4 Hz, 2H, ArB3,5), 6.07 (d, J = 5.6 Hz, 1H, ArC2), 5.98 (d,
J = 5.6 Hz, 1H, ArC6), 5.62 (d, J = 6.4 Hz, 2H, ArC3,5), 3.74 (s, 3H, OCH3(A8)), 2.82 (sept, J = 6.8
Hz, 1H, CHC7), 2.31 (s, 3H, CH3(C10)), 1.29 (d, J = 6.8 Hz, 3H, CH3(C8)), 1.28 (d, J = 6.8 Hz, 3H,
CH3(C9)). 13C{1H} NMR [(CD3)2CO, 100 MHz]: δ 170.1 (CA7), 160.0 (d, JCF = 240 Hz, CB4),
146.0 (CA1), 144.7 (d, JCF = 2 Hz, CB1), 131.8 (CA5), 129.7 (CA3), 124.4 (CA4), 123.4 (CA6), 123.3
(CA2), 119.4 (d, JCF = 8 Hz, CB2,6), 116.2 (d, JCF = 23 Hz, CB3,5), 103.9 (CC1), 102.7 (CC4), 82.5
(CC6), 82.0 (CC2), 80.5 (CC3), 80.2 (CC5), 52.3 (CA8), 32.5 (CC7), 22.8 (CC8), 22.7 (CC9), 19.2
(CC10). HRMS (ESI-TOF) m/z: [M + Na]+ Calcd for C24H25ClFN3O2RuNa 566.0558; Found
566.0564. Anal. Calc. for C24H25ClFN3O2Ru (543.07): C, 53.09; H, 4.64; N, 7.73. Found: C,
52.92; H, 4.57; N, 7.29%.
7

2.3.2. [Ru{1-(2'-methoxycarbonylphenyl)-3-(4'-chlorophenyl)triazenide}(Cl)(p-cymene)] (7)
Complex 7 was prepared in the same manner as complex 6, using triazene 2 (47.2 mg,
0.1633 mmol, 2.0 eq). Yellow crystals (64.9 mg, 0.1160 mmol, 71%). MP = 145-147 ºC.
1
IR(ATR): 3062, 2970, 1716, 1480, 1598, 1448, 1300, 1227, 1089, 833, 753 cm–1. H NMR
[CDCl3, 400 MHz]: δ 7.46 (td, J = 8.4, 1.6 Hz, 1H, ArA5), 7.40 (dd, J = 7.6, 1.2 Hz, 1H, ArA3),
7.29 (d, J = 8.4 Hz, 1H, ArA6), 7.27 (d, J = 8.8 Hz, 4H, ArB2,6,B3,5), 7.15 (td, J = 7.6, 1.2 Hz, 1H,
ArA4), 6.06 (d, J = 6.4 Hz, 1H, ArC2), 5.98 (d, J = 6.4 Hz, 1H, ArC6), 5.63-5.60 (m, 2H, ArC3,5),
3.74 (s, 3H, OCH3(A8)), 2.82 (sept, J = 6.8 Hz, 1H, CHC7), 2.30 (s, 3H, CH3(C10)), 1.28 (d, J = 6.8
Hz, 3H, CH3(C8)), 1.27 (d, J = 6.8 Hz, 3H, CH3(C9)). 13C{1H} NMR [(CD3)2CO, 100 MHz]: δ
170.0 (CA7), 146.9 (CB1), 145.8 (CA1), 131.8 (CA5), 129.7 (CA3), 129.5 (CB3,5), 129.4 (CA2), 124.8
(CA4), 123.5 (CA6), 123.4 (CB4), 119.3 (CB2,6), 103.9 (CC1), 102.8 (CC4), 82.5 (CC6), 82.0 (CC2),
80.5 (CC3), 80.2 (CC5), 52.3 (CA8), 32.5 (CC7), 22.8 (CC8), 22.7 (CC9), 19.2 (CC10). HRMS (ESI-
TOF) m/z: [M + Na]+ Calcd for C24H25Cl2N3O2RuNa 582.0260; Found 582.0265. Anal. Calc. for
C24H25Cl2N3O2Ru (559.04) + C3H6O (acetone) : C, 52.51; H, 5.06; N, 6.80. Found: C, 52.76; H,
5.02; N, 6.50%.
2.3.3. [Ru{1-(2'-methoxycarbonylphenyl)-3-(4'-bromophenyl)triazenide}(Cl)(p-cymene)] (8)
Complex 8 was prepared in the same manner as complex 6, using triazene 3 (54.4 mg,
0.1633 mmol, 2.0 eq). Yelow crystals (69.1 mg, 0.1144 mmol, 70%). MP = 150-155 ºC.
1
IR(ATR): 3061, 2971, 1717, 1598, 1478, 1449, 1300, 1227, 1067, 831, 753 cm–1. H NMR
[(CD3)2CO, 400 MHz]: δ 7.47 (td, J = 7.2, 1.6 Hz, 1H, ArA5), 7.44 (d, J = 8.8 Hz, 2H, ArB3,5),
7.41 (dd, J = 7.6, 1.2 Hz, 1H, ArA3), 7.28 (dd, J = 8.0, 0.8 Hz, 1H, ArA6), 7.21 (d, J = 8.8 Hz,
8

2H, ArB2,6), 7.17 (td, J = 7.6, 1.2 Hz, 1H, ArA4), 6.08 (d, J = 5.6 Hz, 1H, ArC2), 5.98 (d, J = 5.6
Hz, 1H, ArC6), 5.62-5.60 (m, 2H, ArC3,5), 3.75 (s, 3H, OCH3(A8)), 2.82 (sept, J = 6.8 Hz, 1H,
CHC7), 2.31 (s, 3H, CH3(C10)) 1.29 (d, J = 6.8 Hz, 3H, CH3(C8)), 1.28 (d, J = 6.8 Hz, 3H, CH3(C9)).
13C{1H} NMR [(CD3)2CO, 100 MHz]: δ 170.2 (CA7), 147.4 (CB1), 145.8 (CA1), 132.5 (CB3,5),
131.8 (CA5), 129.8 (CA3), 124.8 (CA4), 123.6 (CA6), 123.4 (CA2), 119.7 (CB2,6), 117.1 (CB4), 104.0
(CC1), 102.8 (CC4), 82.5 (CC6), 82.1 (CC2), 80.6 (CC3), 80.3 (CC5), 52.3 (CA8), 32.5 (CC7), 22.8
(CC8), 22.7 (CC9), 19.4 (CC10). HRMS (ESI-TOF) m/z: [M
+
Na]+ Calcd for
C24H25ClBrN3O2RuNa 627.9745; Found 627.9749. [M – Cl]+ Calcd for C24H25BrN3O2Ru
570.0164; Found 570.0165.
2.3.4. [Ru{1-(2'-methoxycarbonylphenyl)-3-(4'-iodophenyl)triazenide}(Cl)(p-cymene)] (9)
Complex 9 was prepared in the same manner as complex 6, using triazene 4 (62.2 g,
0.1633 mmol, 2.0 eq). Yellow crystals (78.0 mg, 0.1198 mmol, 74%). MP = 158-160 ºC.
IR(ATR): 3062, 2947, 1712, 1594, 1574, 1474, 1444, 1300, 1299, 1124, 1067, 834, 753 cm–1.
1H NMR [(CD3)2CO, 400 MHz]: δ 7.63 (d, J = 8.8 Hz, 2H, ArB3,5), 7.47 (td, J = 7.6, 1.6 Hz, 1H,
ArA5), 7.41 (dd, J = 7.6, 1.2 Hz, 1H, ArA3), 7.28 (dd, J = 8.0, 1.2 Hz, 1H, ArA6), 7.18 (td, J = 7.6,
1.2 Hz, 1H, ArA4), 7.08 (d, J = 8.8 Hz, 2H, ArB2,6), 6.10 (d, J = 6.0 Hz, 1H, ArC2), 6.00 (d, J =
6.0 Hz, 1H, ArC6), 5.63-5.60 (m, 2H, ArC3,5), 3.75 (s, 3H, OCH3(A8)), 2.82 (sept, J = 6.8 Hz, 1H,
CH3(C7)), 2.32 (s, 3H, CH3(C10)), 1.29 (d, J = 6.8 Hz, 3H, CH3(C8)), 1.28 (d, J = 6.8 Hz, 3H,
CH3(C9)). 13C{1H} NMR [(CD3)2CO, 100 MHz]: δ 170.0 (CA7), 148.0 (CB1), 146.0 (CA1), 138.7
(CB3,5), 131.9 (CA5), 129.9 (CA3), 125.0 (CA4), 123.7 (CA6), 123.5 (CA2), 120.2 (CB2,6), 104.2
(CC1), 103.0 (CC4), 87.7 (CB4), 82.6 (CC6), 82.2 (CC2), 80.7 (CC3), 80.4 (CC5), 52.4 (CA8), 32.6
(CC7), 22.9 (CC8), 22.8 (CC9), 19.3 (CC10). HRMS (ESI-TOF) m/z: [M + Na]+ Calcd for
C24H25ClIN3O2RuNa 673.9619; Found 673.9621. [M – Cl]+ Calcd for C24H25IN3O2Ru 616.0036;
Found 616.0040. Anal. Calc. for C24H25ClIN3O2Ru (650.97): C, 44.29; H, 3.87; N, 6.46. Found:
C, 44.31; H, 3.84; N, 6.16%.
2.3.6. [Ru{1-(2'-methoxycarbonylphenyl)-3-(4'-methylphenyl)triazenide}(Cl)(p-cymene)] (10)
9

Complex 10 was prepared in the same manner as complex 6, using triazene 5 (43.9 mg,
0.1633 mmol, 2.0 eq). Yellow crystals (81.0 mg, 0.1502 mmol, 93%). MP = 129-132 ºC.
IR(ATR): 3064, 2970, 2939, 1720, 1593, 1447, 1297, 1094, 759 cm–1. 1H NMR [(CD3)2CO, 400
MHz]: δ 7.43 (td, J = 8.4, 1.6 Hz, 1H, ArA5), 7.35 (dd, J = 7.6, 1.2 Hz, 1H, ArA3), 7.23 (dd, J =
8.4, 0.8 Hz, 1H, ArA6), 7.18 (d, J = 8.4 Hz, 2H, ArB2,6), 7.14 (td, J = 7.6, 1.2 Hz, 1H, ArA4), 7.10
(d, J = 8.4 Hz, 2H, ArB3,5), 6.04 (d, J = 5.6 Hz, 1H, ArC6), 5.96 (d, J = 5.6 Hz, 1H, ArC2), 5.59 (d,
J = 6.4 Hz, 1H, ArC3,5), 3.74 (s, 3H, OCH3(A8)), 2.79 (sept, J = 6.8 Hz, 1H, CHC7), 2.30 (s, 3H,
CH3(C10)), 2.29 (s, 3H, CH3(B7)), 1.29 (d, J = 6.8 Hz, 6H, CH3(C8)), 1.28 (d, J = 6.8 Hz, 6H,
CH3(C9)). 13C{1H} NMR [(CD3)2CO, 100 MHz]: δ 170.3 (CA7), 146.2 (CA1), 145.9 (CB1), 134.7
(CB4), 131.7 (CA5), 130.1 (CB3,5), 129.7 (CA3), 124.0 (CA4), 123.2 (CA2), 123.1 (CA6), 118.0
(CB2,6), 103.7 (CC1), 102.7 (CC4), 82.5 (CC2), 82.1 (CC6), 80.5 (CC5), 80.2 (CC3), 52.2 (CA8), 32.5
(CC7), 22.8 (CC8), 22.7 (CC9), 20.9 (CB7), 19.2 (CC10). HRMS (ESI-TOF) m/z: [M + Na]+ Calcd
for C25H28ClN3O2RuNa 562.0809; Found 562.0804.
2.4. X-ray crystallography
A suitable single crystal of
were collected with an Oxford Diffraction Gemini "A" diffractometer with a CCD area
detector, with radiation source of λMoKα = 0.71073 Å for and 10 and λCuKα
1.54184 Å and using graphite-monochromatized radiation at 298 K for and 10, and 130
K for and . Unit cell parameters were determined with a set of three runs of 15
frames (1° in ). The double pass method of scanning was used to exclude any noise.
1, 3, 4, 6, 9 and 10 was mounted on a glass fiber and data
3,
4
,
6,
9
=
9
1,
3
,
4
6
ω
The collected frames were integrated by using an orientation matrix determined from the
narrow frame scans. CrysAlisPro and CrysAlis RED software packages were used for
data collection and integration [35]. The double pass method of scanning was used to
exclude any noise. The collected frames were integrated by using an orientation matrix
determined from the narrow frame scans. Final cell constants were determined by a
10

global refinement; collected data were corrected for absorbance by using analytical
numeric absorption correction using a multifaceted crystal model based on expressions
upon the Laue symmetry using equivalent reflections [36]. Structure solution and
refinement were carried out with the SHELXS-2014 and SHELXL-2014 packages [37];
WinGX v2014.1 software was used to prepare material for publication [38,39]. Full-
matrix least-squares refinement was carried out by minimizing (Fo2 - Fc2)2. All
nonhydrogen atoms were refined anisotropically and the refinement was carried out
without restraint. The H atom of the amine group was located in a difference map and
refined isotropically with Uiso(H) = 1.2 for H–N. Hydrogen atoms attached to carbon
atoms were placed in geometrically idealized positions and refined as riding on their
parent atoms, with C—H = 0.93–0.98 Å with Uiso (H) = 1.2 Ueq(C) for methyne and
aromatic groups, and Uiso (H) = 1.5 Ueq(C) for methyl group.
A suitable crystal of compound 2 was mounted on a glass fiber at room temperature,
then placed on a Bruker SMART APEX CCD-based X-ray diffractometer system equipped with
a Mo-target X-ray tube (λMoKα = 0.71073 Å). The detector was placed at a distance of 5.0 cm
from the crystals, in all cases decay was negligible. A total of 2400 frames were collected with a
scan width of 0.3 in x and an exposure time of 10 s/frame. The frames were integrated with the
Bruker SAINT Software package using a narrow-frame integration algorithm. Systematic
absences and intensity statistics were used in space group determination. The structure was
solved using direct methods using SHELXS-2014/7 program [40]. Anisotropic structure
refinements were achieved using full matrix, least-squares technique on all non-hydrogen
atoms. All hydrogen atoms were placed in idealized positions, based on hybridization, with
isotropic thermal parameters fixed at 1.2 times the value of the attached atom. Structure
refinements were performed using SHELXL-2014/7 [40].
11

The crystal structure is almost planar, azido frame is making dihedral angles of 4.5 (2)° and 4.9
(2)° with the aromatic ring (C1-C6) and (C9-C14), the dihedral angle between phenyl ring was
7.3 (2 )°.
2.5. General procedure for transfer hydrogenation studies monitored by 1H NMR
All measurements were made on a Bruker 400 spectrometer operating at 400 MHz.
Inside a nitrogen glovebox acetophenone (6 × 10–5 mol), 1,3,5-trimethylbenzene (2 µL) as
internal standard and 0.6 mL of 2-propanol-d8 were transferred into a J-Young NMR tube. The
1
tube was closed in order to avoid air contamination, and a H NMR spectrum was recorded.
Next, the tube was brought back into the glovebox and the ruthenium precatalyst (1.2 × 10–6
mol) and KOH (6 × 10–6 mol only for base-assisted reactions) were added. Outside of the
glovebox the tube was placed in an oil bath at 70 °C. At the desired sampling time, the tube was
1
taken out of the oil bath, and a H NMR spectrum was recorded. Percent conversions were
determined by comparing the integration of the aromatic protons at the ortho position of the
alcohol with the aromatic protons at the ortho position of the acetophenone. The value of the
integral for the singlet due to the aromatic protons of 1,3,5-trimethylbenzene (internal standard)
was set equal to 10 units in each case.
2.6 General procedure for catalytic transfer hydrogenation monitored by Gas
Chromatography-Mass Spectrometry (GC-MS).
Ruthenium precatalyst (1.2 × 10–6 mol), acetophenone (6 ×10–5 mol), 2-propanol (0.6
mL) and KOH (6 × 10–6 mol only for base-assisted reactions) were transferred into a 1.5 mL
vial. The resulting solution was heated at 70 ºC and the reaction progress was monitored by GC-
MS analysis in order to calculate the conversion of the substrate. At the desired sampling time,
an aliquot of 0.1 mL was taken and diluted to 1.0 mL with 2-propanol.
The analytical GC-MS system used was an Agilent 7890A GC coupled to 5975C Mass
detector Agilent Technologies, equipped with a HP-5MS capillary column (30 m × 0.25 mm ×
0.25 micron) Agilent Technologies, Inc. An Agilent Technologies 7693 auto sampler was used
to inject 1 µL of a solution sample. The ionization energy was 70 eV with a mass range of 30 to
12

800 m/z. The initial temperature of the column was set at 80 ºC, held for 2 min, and then a ramp
of 15 ºC/min to 250 ºC. The temperature of the injector was set at 250 ºC and the detector to 230
ºC. The flow rate of the carrier gas (Helium) was 1.0 mL/min injected with a gas dilution of
1:50. Identification of the individual components was based on comparison with the mass
spectra library (NIST98).
3. Results and discussion
3.1. Synthesis and general characterization
3.1.1. Triazenes
Triazene 5 was synthesized according to previously reported procedure [15], while
triazenes 1-4 were synthesized following modified literature procedures [41] by diazotization of
methyl antranilate with sodium nitrite, followed by coupling with the corresponding
p-substituted aniline. The structures with atom labeling of triazenes 1-4 are shown in Fig. 3.
Figure 3. Structure and labeling of triazenes 1-4.
The IR spectra of triazenes 1-4 show bands in common in the range of 3243-3188 cm–1
for the N-H group, 1582-1576 cm–1 for the N3 system and at 1685 cm–1 for the C=O group.
The 1H NMR spectra of triazenes 1-4 show a broad singlet at low field in the range of
12.33-12.42 ppm assigned to the triazene N-H group. In the aromatic region of each triazene,
there are two doublets and two triplets at ~8.01, ~7.89, ~7.52 and ~7.03 ppm, respectively,
which correspond to the ortho-disubstituted aromatic ring (A). On the other hand, the two
doublets of the para-disubstituted aromatic ring (B) appear at different chemical shifts as a
result of differences in the electronegativity of the para-substituent. For example, the signal of
the equivalent hydrogen atoms B3 and B5 appears at 7.10, 7.35, 7.52 and 7.72 ppm for triazenes
1 (p-F), 2 (p-Cl), 3 (p-Br), and 4 (p-I), respectively (Fig. 4). These results are in agreement with
13

the experimental and calculated chemical shifts of a related triazene [42]. The signal of the
methoxy group (OCH3) appears as a singlet at ~3.93 ppm, which integrates for three hydrogens.
The 13C NMR spectra of triazenes 2-4 show 10 signals for the carbon atoms in the aromatic
region, a carbonyl signal at 167.7 ppm, and a methoxy signal at ~52.2 ppm for the ortho-
methoxycarbonyl group. On the other hand, in the 13C NMR spectrum of triazene 1, the carbons
B4 (163.2 ppm), B3,5 (116.7 ppm), B2,6 (124.2 ppm) and B1 (147.1 ppm), appear as doublets
with coupling constants of 244.3, 22.7, 9.0 and 3.0 Hz, respectively, due to their coupling with
the p-F substituent. Interestingly, the inductive effect of the halogen substituent affects the
chemical shift of carbon B4 [43], which is shifted downfield as the halogen bonded to carbon
B4 becomes more electronegative, appearing at 163.2, 133.4, 121.5 and 93.0 ppm for triazenes
1 (p-F), 2 (p-Cl), 3 (p-Br), and 4 (p-I), respectively.
Figure 4. 1H NMR spectra of the aromatic region of triazenes 1-4.
14

3.1.2. Ruthenium Complexes
Reaction of 1,3-bis(aryl)triazene ligand precursors 1-5 with half equivalent of [RuCl(p-
cymene)(µ-Cl)]2 in dichloromethane at room temperature and in the presence of triethylamine,
resulted in the formation of new monomeric [RuCl(η2-1,3-ArNNNAr)(η6-p-cymene)]
complexes 6-10 (Eq. (1)).
Complexes 6-10 were isolated as stable yellow solids. Their formulation is supported by
analytical and spectroscopic data (IR, NMR and HRMS), and X-ray crystal structure
determination.
The IR spectra show bands in the range of 1598-1593 and 1720-1716 cm–1 for the
triazenide (N3) system and carbonyl group, respectively. The ν(C=O) bands undergo positive
shifts with respect to the triazenes 1-5, suggesting that the carbonyl group remains
uncoordinated [44-46].
In the 1H NMR spectra of 6-10, the triazenide ligands give signals for ortho and para-
disubstituted aromatic rings shifted 0.1-0.6 ppm downfield, in comparison with their respective
free triazenes 1-5. The methoxy group is observed as a singlet at ~3.75 ppm. In the 13C NMR
spectra of complexes 6-10, no significant shifts were observed compared to the free triazenes 1-
5.
Interestingly, the presence of a chiral center in the metal complexes 6-10 due to the
1
coordination of the unsymmetric triazenide ligands from 1-5, is clearly reflected in their H
NMR spectra. The p-cymene aromatic protons are observed as two doublets in the range of
6.10-5.70 ppm (J = ~6.0 Hz) and two overlapped doublets at ~5.62 ppm, which is typical in
RuII(p-cymene) complexes where the metal is a chiral center [47-51]. With symmetric triazenide
15

ligands in RuII(p-cymene)triazenide complexes previously reported [19-21], these aromatic
protons are two by two equivalent, leading to only two signals in the spectra. Also, the isopropyl
methyl protons are inequivalent, appearing as two doublets (J = ~6.8 Hz) at ~1.29 and ~1.28
ppm. In the 13C NMR spectra, the signals for the isopropyl methyl carbons are observed as two
signals at ~22.8 and ~22.7 ppm, while the p-cymene aromatic carbons are observed as six
signals in the range of 104.0-80.2 ppm. The NMR assignments were confirmed by gCOSY,
gHSQC and gHMBC experiments (see Supporting Information). Complexes 6-10 were
analyzed by HRMS (ESI-TOF) and their spectra showed the formation of adducts of the type
[M + Na]+, which may be a consequence of using sodium formate as calibrant.
3.2. Description of the crystal structures
Crystals of triazenes 1-4 suitable for X-ray diffraction studies were obtained. Triazenes
3 and 4 crystallized in the triclinic crystalline system while 1 and 2 in the monoclinic and
orthorhombic system, respectively, with different space groups (P 21/n for 1, P 21 21 21 for 2,
and P-1 for 3 and 4).
Since the structures of triazenes 1-4 are analogous, only the ORTEP diagram of triazene
1 in Fig. 5 is shown as an example. The ORTEP diagrams of triazenes 2-4 and the crystal data
for these compounds are given in the Supporting information (Figures S1-3 and Table S1,
respectively), while selected bond distances and angles are listed in Table 1. Triazenes 1-4 adopt
trans configuration about the N=N double bond. The N(1)-N(2) and N(2)=N(3) bond lengths
are ca. 1.34 and 1.26 Å, respectively, which indicates the presence of single and double bonds.
The N(1)-N(2)=N(3) bond angles are ca. 111.0°, whereas the dihedral angle between the two
aromatic rings at 5.68, 7.27, 13.04 and 14.89°, for triazenes 1-4, respectively, seems to be
affected by the electronegativity of the para-substituent. The bond distances and angles are in
agreement with those reported for related triazenes with ortho and para-halogen substituents
[52-58]. On the other hand the distances and angles of the o-methoxycarbonyl substituent are in
agreement with those reported for related triazenes [59,60].
16

Figure 5. ORTEP diagram for triazene 1 with thermal ellipsoids drawn at 50% probability
level.
Table 1. Selected bond distances (Å) and angles (°) for triazenes 1-4.
Bond distances (Å)
1 (X = F)
1.347(4)
1.270(5)
0.907(19)
1.397(5)
1.425(5)
1.368(4)
1.232(5)
1.341(4)
1.446(5)
2 (X = Cl)
1.340(2)
1.261(2)
0.915(9)
1.378(3)
1.418(3)
1.740(2)
1.202(3)
1.330(3)
1.434(2)
Angles (°)
112.1(2)
113.1(2)
121.3(2)
120.7(15)
123.3(3)
3 (X = Br)
1.345(3)
1.264(3)
0.896(17)
1.384(3)
1.424(3)
1.903(3)
1.215(3)
1.337(3)
1.449(3)
4 (X = I)
1.334(5)
1.262(4)
0.81(4)
1.389(5)
1.414(5)
2.108(4)
1.213(4)
1.345(5)
1.445(5)
N(1)-N(2)
N(2)-N(3)
N(1)-H(1D)
C(7)-N(1)
C(1)-N(3)
C(4)-X
C(13)=O(1)
C(13)-O(2)
C(14)-O(2)
N(3)-N(2)-N(1)
N(2)-N(3)-C(1)
N(2)-N(1)-C(7)
N(2)-N(1)-H(1D)
O(1)-C(13)-O(2)
111.1(3)
111.6(3)
119.4(3)
122(3)
111.0(2)
112.5(2)
120.2(2)
119.4(18)
121.6(3)
112.3(3)
112.1(3)
120.6(4)
121(3)
121.6(4)
121.8(4)
Crystals of the triazenide ruthenium complexes 6, 9 and 10 suitable for X-ray diffraction
were obtained by vapor phase diffusion of hexane into concentrated solutions of the complexes
in tetrahydrofuran. Complexes 6 and 9 crystallized in the monoclinic crystalline system while
10 in the orthorhombic system, with different space groups (P 21/n, P 21/c and P 21 21 21,
respectively).
17

The ORTEP diagrams of complexes 6, 9 and 10 are given in Figs. 6-8 with selected
bond lengths and angles. The crystal data for these compounds are given in the Supporting
information, (Table S2). In the complexes the ruthenium atom is surrounded by the η6-bonded
p-cymene ring, a chelating η2-triazenide ligand and one chloro ligand, attaining a pseudo-
octahedral ¨three legged piano stool¨ geometry. The small-bite of the triazenide [N(1)-Ru-N(2)]
of ca. 59.0°, influence the bond angles around the metal, but only those affecting this ligand, in
such a way that the N-Ru-Cl angles are all close to the expected 90°. The Ru-N distances are ca
2.06 Å, while the N-N bond lengths in the triazenide systems are ~1.31 Å, a value which is
between a single (N-N) and a double bond (N=N). All these values are in the range found for
previously reported RuII(p-cymene)triazenide complexes [18-21].
Figure 6. ORTEP diagram for compound 6 with thermal ellipsoids drawn at 60% probability
level. Bond distances (Å): Ru-N1, 2.067(2); Ru-N3, 2.084(2); N(1)-N(2), 1.306(3); N(2)-N(3),
1.314(3); N(1)-C(1), 1.398(3); Ru-Cl1, 2.3897(7); Ru-CT, 1.668; C(7)=O(1), 1.211(5); C(12)-
F(1), 1.370(3). Bond angles (°): N(1)-N(2)-N(3), 103.0(2); N1-Ru-N3, 59.19(8); Cl-Ru-N1,
85.51(6); Cl-Ru-N3, 87.83(7); O(2)-C(13)=O(1), 122.8(3).
18

Figure 7. ORTEP diagram for the compound 9 with thermal ellipsoids drawn at 40%
probability level. Bond distances (Å): Ru-N1, 2.076(2); Ru-N3, 2.074(2); N(1)-N(2), 1.303(3);
N(2)-N(3), 1.316(3); N(1)-C(1), 1.409(3); Ru-Cl1, 2.3895(8); Ru-CT, 1.675; C(7)=O(1),
1.199(4); C(12)-I(1), 2.102(3). Bond angles (°): N(1)-N(2)-N(3), 102.3(2); N1-Ru-N3,
58.84(10); Cl-Ru-N1, 87.46(7); Cl-Ru-N3, 83.77(7); O(2)-C(7)=O(1), 125.1(3).
Figure 8. ORTEP diagram for compound 10 with thermal ellipsoids drawn at 40% probability
level. Bond distances (Å): Ru-N1, 2.066(4); Ru-N3, 2.089(4); N(1)-N(2), 1.312(5); N(2)-N(3),
1.322(6); N(1)-C(1), 1.400(6); Ru-Cl(1), 2.3921(13); Ru-CT, 1.671; C(7)=O(1), 1.193(8). Bond
angles (°): N(1)-N(2)-N(3), 102.0(4); N1-Ru-N3, 59.03(16); Cl-Ru-N1, 84.76(12); Cl-Ru-N3,
85.44(11); O(2)-C(7)=O(1), 123.4(7).
19

These complexes display interesting crystal arrangements. For example, complex 6
exhibits C-H···Cl, C-H···F and C-H···π important intermolecular hydrogen bonding
interactions that define the crystal arrangement. The C9-H9···Cl [2.907 Å, 158.6°] interaction
gives place to the formation of a centrosymmetric 14-member ring shown in Fig. 9. In addition,
the Cl atom presents a second C-H···Cl interaction with H3 [2.86, 137°], which together with
the C4-H4···πC7-C12 [2.99 Å, 130°] interactions produces a 10-member cycle (Fig. 9). Thus, both
the 14-member and the 10-member rings form a 2D-supramolecular arrangement shown in Fig.
10. The supramolecular framework is completed by C24-H24A···F [2.76 Å, 117.5°] and C19-
H19···πC1-C6 [2.88 Å, 111°] interactions.
Figure 9. Representation of the 14-member (a) and 10-member (b) rings in complex 6.
Hydrogen atoms not involved have been omitted for clarity.
20

Figure 10. Representation of the 2D arrangement in complex 6. Only the hydrogen atoms
involved in the non covalent interactions have been drawn.
3.3. Transfer hydrogenation catalysis
To investigate the effects of the presence of different para-substituted triazenide ligands
on the reactivity, complexes 6-10 were tested for their ability to catalyze the reduction of
acetophenone to 1-phenylethanol under the conditions shown in Eq. (2).
O
OD
Complex (2%)
(2)
KOH, 2-Propanol-d8
70 oC
21

Table 2. Transfer hydrogenation of acetophenone using 6-10 as pre-catalysts.a
Entry
1
Pre-cat.
S/Cat/KOH Time (h)
Yield (%)b
65
100:2:0
100:2:0
100:2:0
100:2:0
100:2:0
100:2:10
100:2:10
100:2:10
100:2:10
100:2:10
24
24
24
24
24
12
12
12
12
12
6
2
3
60
45
42
48
94
92
89
86
92
7
8
4
9
5
10
6
6
7
7
8
8
9
9
10
10
a Reaction conditions: 2-propanol-d8, 70 °C, with or without KOH as base. bYields were determined by 1H NMR.
The results of the catalytic evaluation in the absence or in the presence of base are
summarized in Table 2. Among pre-catalysts 6-9 with different p-halogen substituents, 6 with
the p-F substituent in the 1,3-bis(aryl)triazenide ligand shows the best activity of transfer
hydrogenation under base-free conditions, with a yield of 65% after 24 h of reaction (entry 1),
whereas, 7 (p-Cl), 8 (p-Br) and 9 (p-I) show yields of 60, 45, and 42%, respectively (entries 2-
4). These results indicate that the presence of a more electronegative p-halogen substituent in
the 1,3-bis(aryl)triazenide ligand enhance the activity of the catalyst. This trend contrasts with
O'connor's [(pyridinesulfonamide)Ir(Cp*)] catalyst system in which the transfer hydrogenation
reactivity decreases with electron-withdrawing groups on the ligand [24]. Interestingly, pre-
catalyst 10 (p-CH3) is slightly more active than 8 (p-Br) and 9 (p-I), with a yield of 48% (entry
5) under the same conditions. This result was unexpected since the p-CH3 group is less
electronegative (a σ donor). However, it is difficult to compare the electronic effects between p-
CH3 and the p-halogen substituents since the halogens are σ acceptors and also π donors [43].
As can be observed in Fig. 11, no induction period was detected in any case, since production of
1-phenylethanol begins to form immediately after thermal equilibration of the reactant mixture.
22

70
60
50
40
30
20
10
0
6
7
8
9
10
0
5
10
15
20
25
30
t (h)
Figure 11. Reaction profile of conversion vs time for the catalytic transfer hydrogenation of
acetophenone under base-free conditions, monitored by 1H NMR.
When an external base is used, higher yields are obtained in shorter times, and the
difference in reactivity between pre-catalyst decreases. For example, with the fastest pre-
catalyst 6 and the slowest pre-catalyst 9, conversions of 94 and 86%, respectively, are achieved
after 12 h of reaction (Fig. S6).
Interestingly, the conversion obtained with pre-catalyst 6 in the presence of base is
exactly the same than the conversion previously reported with pre-catalyst A (Fig. 2) under the
same conditions (94% in 12 h) [21]. In contrast, when no external base is used the activity
between 6 and A changed drastically, since a higher yield was obtained with A under the same
conditions (65 vs 86%, respectively, in 24 h) [21]. It seems that under base-free conditions, the
presence of a second o-methoxycarbonyl substituent in the triazenide ligand of A enhance the
catalytic activity, probably by increasing the possibility of weak interactions between the
hydride and the ortho-substituent with the substrate molecule [61]. Additionally, increasing the
steric bulk of the ligand [22,23], probably brings the -COOCH3 group close to the external
coordination sphere of the ruthenium center more effectively [61]. Further studies would be
needed to explain the role of the ortho- and para-substituents in the catalysis. However,
experimental and computational studies by Jiménez et. al. showed that for Ir(I) carbene transfer
23

hydrogenation catalysts the presence of a pendant oxygen donor group enhance the catalytic
activity through O···H interactions rather than oxygen to metal coordination [61].
Table 3. Transfer hydrogenation of acetophenone using 6 as pre-catalysts with different
changes in the reaction media.a
Entry
1
Additive
p-cymene
Additive/cat. ratio S/Cat/KOH Time (h)
Yield (%)b
95
40/1
40/1
300/1
300/1
1/1
100:2:10
100:2:0
100:2:10
100:2:0
100:2:0
12
24
12
24
24
2
3
4
5
p-cymene
Hg
66
89
Hg
61
HCl
1%
b
a Reaction conditions: 2-propanol, 70 °C, with or without KOH as base. Yields were determined by GC-MS.
Additional experiments were carried out with complex 6 as pre-catalyst in order to
obtain information on the mechanism operating in the absence of base. First, a mercury
poisoning experiment was conducted to test for heterogeneous catalysis (Table 3, entry 4).
There was no significant impact on conversion from the addition of Hg(0); thus it is unlikely
that heterogeneous sources of Ru are responsible for the activity observed [62].
Since one of the possible activation pathways could be decoordination of the p-cymene,
an experiment in which free p-cymene was added to the reaction medium was run (Table 3,
entry 2). The fact that an inhibition of the catalytic activity did not occur, indicates that
decoordination of the arene does not occur during the catalytic process [22].
The same conclusions with the mercury poisoning experiment and the addition of free
p-cymene have been obtained for the reaction in the presence of base (Table 3, entries 3 and 1,
respectively).
Finally, the formation of hydrides in the absence or in the presence of base in 2-
propanol was explored. First, pre-catalyst 6 in 2-propanol was heated at 70 °C in the presence of
base. After 10 min of reaction the solvent was evaporated and a 1H NMR spectrum in dry C6D6
−12.52 ppm.
was recorded. A hydride signal was detected at
In contrast, in the absence of base,
1
after 6 h of reaction and treated in the same manner, the H NMR spectrum showed two
−10.77 ppm. It is also noteworthy that a broad resonance
different hydride signals at −8.79 and
24

at low field (12.88 ppm), which can be ascribed to an NH group of the ligand, is also observed
(free triazene 1 is not present in the reaction mixture).
These differences of activity in the presence or in the absence of base point to different
reaction mechanisms for base-free and base-assisted catalysis. In the presence of base an inner-
sphere mechanism is proposed [63]. On the other hand, based on what was found in the recent
literature for transfer hydrogenation reactions under base-free conditions [25], an outer-sphere
mechanism as shown in Scheme S1 (see Supporting information), in which one of the triazenide
nitrogens acts as a base, is proposed. Theoretical calculations can be employed to her investigate
mechanistic details. However, this is beyond the scope of
4. Conclusions
A series of four new triazenes of the type 1-[2'-(methoxycarbonyl)phenyl]-3-[4'-X-
phenyl]triazene (X = F, Cl, Br, I) as precursors of triazenide ligands have been synthesized and
characterized by IR, NMR and MS, and molecular structures determined by X-ray diffraction
studies. Their corresponding ruthenium(II) complexes of formulae [Ru{1-(2'-
methoxycarbonylphenyl)-3-(4'-X-phenyl)triazenide}(Cl)(p-cymene)] (X = F, Cl, Br, I, CH3)
were subsequently prepared and fully characterized by IR, NMR and HRMS. X-ray crystal
structures of complexes 6 (X = F), 9 (X = I) and 10 (X = CH3) were determined, which show
common features with other RuII(p-cymene)triazenide complexes. Compounds 6-10 were tested
in the catalytic reduction of acetophenone to 1-phenylethanol, either in the presence or the
absence of a base. The best results were obtained in the presence of base with yields in the range
of 86-94 %, whereas in the absence of base lower yields in the range 42-65% were achieved.
This points to different reaction mechanisms: in the absence of base, an outer-sphere mechanism
has been proposed [25], whereas in the presence of base an inner-sphere mechanism is proposed
[63]. It is important to notice that although the yields are moderate in the absence of base, it is a
good result since most pre-catalysts require a base to form the hydride complex as the active
catalyst [26-30]. As hypothesized complexes 6-9 are active catalysts in the transfer
hydrogenation of acetophenone. Their efficiency is dependent on the p-substituent with the p-F
substituted being the most active in both base-free and base-assisted hydrogenations.
25

Acknowledgements
This work was supported by Consejo Nacional de Ciencia y Tecnología (CONACyT)
Grant 60467 and Dirección General de Educación Tecnológica (DGEST) Grant 5150.13-P.
E.C.-A and C.C.-A thank CONACyT for graduate fellowship. We thank CONACyT for ITT
NMR and HRMS facilities (Grants INFR-2011-3-173395 and INFR-2012-01-187686). E.C.-A.
thanks ESET, LLC for complementary financial support.
Appendix A. Supplementary material
CCDC 1538510 (1), 1541365 (2), 1538512 (3), 138513 (4), 138514 (6), 138515 (9),
138511 (10) contains the supplementary crystallographic data for this paper. These data can be
obtained free of charge from The Cambridge Crystallographic Data Centre via
www.ccdc.cam.ac.uk/data_request/cif.
Supplementary data associated with this article can be found, in the online version, at
http://xxxxxxxxxxx
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