Preparation of monocarbonyl ruthenium complexes bearing bidentate nitrogen and phosphine ligands and their catalytic activity in carbonyl compound reduction

Article abstract of DOI:10.1039/c9dt02616a

Monocarbonyl complexes [RuCl₂(CO)(PR₃)(NN)] (R = Cy, NN = en 1, ampy 2; R = iPr; NN = en 3) have been prepared in a one pot reaction from [RuCl₂(CO)(dmf)(PPh₃)₂], PR₃ and the NN ligand in CH₂Cl₂. Treatment of [Ru(OAc)₂(CO)(PPh₃)₂] with NN ligands in methanol gives the cationic derivatives [Ru(OAc)(CO)(PPh₃)(NN)]OAc (NN = en 4, ampy 5) in which one acetate acts as a bidentate ligand, whereas the other is not coordinated. Diphosphine complexes [RuCl₂(CO)(PP)(PPh₃)] (PP = dppb 6, dppf 7, (R)-BINAP 8, (R,S_p)-Josiphos 9 and (R,R)-Skewphos 10) have been obtained starting from [RuCl₂(CO)(dmf)(PPh₃)₂] and the PP ligand in CHCl₃ or toluene at reflux. The reaction of [Ru(OAc)₂(CO)(PPh₃)₂] with PP in CH₂Cl₂ or toluene affords the fluxional acetate derivatives [Ru(OAc)₂(CO)(PP)] (PP = dppb 11, dppf 12, (R)-BINAP 13, and (R,R)-Skewphos 14). The cationic diphosphine complexes [RuCl(CO)(PP)(en)]Cl (PP = dppb 15, dppf 16) are prepared from [RuCl₂(CO)(dmf)(PPh₃)₂], PP and en in CH₂Cl₂ or, alternatively, from [RuCl₂(CO)₂]_n or the 6, 7 derivatives. Similarly, [Ru(OAc)(CO)(PP)(NN)]OAc (PP = dppb, NN = en 17, ampy 18; PP = dppf, NN = en 19, ampy 20) are isolated starting from [Ru(OAc)₂(CO)(PPh₃)₂], PP and NN ligands or from 11, 12. The derivatives [Ru(OAc)₂(CO)(PP)] show a fluxional behavior in solution as the result of the flexible coordination of acetate ligands. These complexes are found to be active in the transfer hydrogenation and hydrogenation of ketones and aldehydes, including furfural derivatives, at an S/C up to 10000 and a TOF up to 18000 h^-1.

Full text of DOI:10.1039/c9dt02616a

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Comuzzi, A. del zotto, R. Figliolia, G. Lippe, D. Lovison, P. Strazzolini, S. Susmel, E. Zangrando, D.
ZUCCACCIA, S. Baldino, M. Ballico and W. Baratta, Dalton Trans., 2019, DOI: 10.1039/C9DT02616A.
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DOI: 10.1039/C9DT02616A
Dalton Transaction
Preparation of Monocarbonyl Ruthenium Complexes Bearing Bidentate Nitrogen and
Phosphine Ligands and their Catalytic Activity in the Carbonyl Compound Reduction
Steven Giboulot,a, b Clara Comuzzi,a Alessandro Del Zotto,a Rosario Figliolia,a Giovanna Lippe,a
Denise Lovison,a Paolo Strazzolini,a Sabina Susmel,a Ennio Zangrando,c Daniele Zuccaccia,a
Salvatore Baldino,a, d Maurizio Ballico,a,* Walter Barattaa,*
a Dipartimento DI4A - Università di Udine, Via Cotonificio 108, I-33100 Udine, Italy
b Johnson Matthey, 28 Cambridge Science Park, Milton Road Cambridge, CB4 0FP, United Kingdom
c Department of Chemical and Pharmaceutical Sciences, University of Trieste, Via Licio Giorgieri,
1, 34127 Trieste, Italy
d Dipartimento di Chimica, Università di Torino, Via Pietro Giuria, 7, I-10125 Torino, Italy
Abstract
The monocarbonyl complexes [RuCl2(CO)(PR3)(NN)] (R = Cy, NN = en 1, ampy 2; R = iPr; NN =
en 3) have been prepared in a one pot reaction from [RuCl2(CO)(dmf)(PPh3)2], PR3 and the NN ligand
in CH2Cl2. Treatment of the [Ru(OAc)2(CO)(PPh3)2] with NN ligands in methanol gives the cationic
derivatives [Ru(OAc)(CO)(PPh3)(NN)]OAc (NN = en 4, ampy 5) in which one acetate acts as
bidentate ligand, whereas the other is not coordinated. The diphosphine complexes
[RuCl2(CO)(PP)(PPh3)] (PP = dppb 6, dppf 7, (R)-BINAP 8, (R,Sp)-Josiphos 9 and (R,R)-Skewphos
10) have been obtained starting from [RuCl2(CO)(dmf)(PPh3)2] and the PP ligand in CHCl3 or toluene
at reflux. Reaction of [Ru(OAc)2(CO)(PPh3)2] with PP in CH2Cl2 or toluene affords the fluxional
acetate derivatives [Ru(OAc)2(CO)(PP)] (PP = dppb 11, dppf 12, (R)-BINAP 13, and (R,R)-
Skewphos 14). The cationic diphosphine complexes [RuCl(CO)(PP)(en)]Cl (PP = dppb 15, dppf 16)
are prepared from [RuCl2(CO)(dmf)(PPh3)2], PP and en in CH2Cl2 or, alternatively, from
[RuCl2(CO)2]n or the 6, 7 derivatives. Similarly, [Ru(OAc)(CO)(PP)(NN)]OAc (PP = dppb, NN = en
17, ampy 18; PP = dppf, NN = en 19, ampy 20) are isolated starting from [Ru(OAc)2(CO)(PPh3)2],
PP and NN ligands or from 11, 12. The derivatives [Ru(OAc)2(CO)(PP)] show a fluxional behavior
in solution as the result of the flexible coordination of acetate ligands. These complexes are found
active in the transfer hydrogenation and hydrogenation of ketones and aldehydes, including furfural
derivatives, at S/C up to 10000 and TOF up to 18000 h-1.

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DOI: 10.1039/C9DT02616A
Introduction
Ruthenium complexes have been widely investigated in the last decades on account of their broad
catalytic activity for a number of organic transformations. In addition to C-C coupling reactions,1, 2
the reduction of the C=O bond via hydrogenation (HY)3-6 and transfer hydrogenation (TH)7-13
reactions promoted by ruthenium catalysts are extensively accepted in the industry as efficient and
environmentally benign way for the preparation of alcohols14 and only few examples have been
demonstrated active in both HY or TH reactions.15-18 The search of the appropriate set of ligands
remains crucial for achieving high selectivity and productivity, which are prerequisites for large-scale
applications. Monocarbonyl ruthenium complexes have attracted a great deal of attention in
homogeneous catalysis on account of their ability to promote several catalytic transformations,
including hydrogenation of carbonyl compounds,19-23 esters and amides,24-28 dehydrogenation of
alcohols,29-38 borrowing hydrogen reactions.39-43 Some relevant examples are shown in Figure 1.
P
P
F2
C
O
Ru CO
PPh2
Cl
PiPr2
PtBu2
PPh3
CO
F2C
Cl
O
H
O
O
H
H
O
N
Ru
N
Ru
Ph3P Ru
CO
CO
O
N
Ru
CO
H
H
H
O
O
O
O
H
O
H
Cl
O
N
NEt2
CF2
PPh2
F3C
O
CF3
OC Ru
O
C
F2
P
P
Gusev
Milstein
Saito
Dobson
Hulshof
Figure 1. Monocarbonyl ruthenium catalysts.
It is worth noting that a number of dicarbonyl ruthenium complexes employed in catalysis have
proven to dissociate one CO, thus resulting in the formation of catalytically active monocarbonyl
complexes.44-48 The presence of a CO ligand on ruthenium may prevent side reactions, such as
decarbonylation of the substrates (i.e. aldehydes), which is regarded as a pathway of catalyst
deactivation.49-51 As far as the preparation of monocarbonyl complexes is concerned,
[RuHCl(CO)(XPh3)3] (X = P, As) and [RuH2(CO)(PPh3)3] are usually employed as suitable
precursors via displacement of PPh3 with strongly coordinating polydentate ligands, or protonation
of the hydride. Recently, we reported the isolation of [RuH(CO)(dppp)(NN)]Cl from
[RuHCl(CO)(PPh3)3] and dppp,52 a reaction which failed when using the related diphosphines dppb
and dppf, thus limiting the scope of this reaction.53 In addition, Batista et al. described a series of

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monocarbonyl Ru complexes with dppb and bipyridine ligands, from [RuCl2(CO)(dppb)]2(dppb),
DOI: 10.1039/C9DT02616A
which display antitumor activity,54, 55 whereas [RuCl2(CO)(PP)]2(PP) have been obtained from
[RuCl2(CO)2]n and PP ligands.56 It is to point out that a systematic and simple approach for the
synthesis of monocarbonyl ruthenium derivatives with different bidentate PP and NN ligands has
been sparingly described in spite of the great interest for PP and NN ruthenium complexes in catalysis
and other applications.
In our ongoing interest in the synthesis of carbonyl ruthenium complexes for homogeneous
catalysis,57, 58 we report herein a general entry for the easy preparation of a series of monocarbonyl
ruthenium complexes containing bidentate nitrogen and diphosphine ligands through straightforward
syntheses starting from [RuCl2(CO)(dmf)(PPh3)2]59 and [Ru(OAc)2(CO)(PPh3)2]60 precursors. The
monocarbonyl phosphine ruthenium complexes, in the presence of primary amine ligands (i.e. en and
ampy61), display catalytic activity in the reduction of ketones and aldehydes at S/C up to 10000.
Results and Discussion
Synthesis of monocarbonyl ruthenium chloride and acetate complexes with NN ligands.
Complexes
having
formula
[RuCl2(CO)(PR3)(NN)]
are
easily
obtained
from
[RuCl2(CO)(dmf)(PPh3)2] by reaction with a phosphine and a bidentate dinitrogen ligand, whereas
the acetate complexes [Ru(OAc)(CO)(PPh3)(NN)]OAc are prepared from [Ru(OAc)2(CO)(PPh3)2]
and a NN ligand. Accordingly, treatment of [RuCl2(CO)(dmf)(PPh3)2] with PCy3 in CH2Cl2 at RT,
followed by reaction with en, affords the complex trans-[RuCl2(CO)(PCy3)(en)] (1), isolated in 89%
yield (Scheme 1). The 1H NMR spectrum of 1 in CD2Cl2 displays two multiplets at δ 3.10 and 2.93
ppm for the methylene groups of the en52 ligand, while the NH2 moieties appear at δ 3.70 and 3.27
13
ppm. The C{1H} NMR doublet at δ 206.0 ppm (2JCP = 16.8 Hz) is attributable the CO carbon,
whereas the doublets at δ 43.5 and 42.3 ppm are for the CH2 groups of en (Table 1). The low νC≡O at
1936 cm-1 in the IR spectrum of 1 is in agreement with the presence of a trans amine and a cis PCy3
62
ligand.19,
Control 31P{1H} NMR experiments carried out after the addition of PCy3 to
[RuCl2(CO)(dmf)(PPh3)2] in CD2Cl2 at RT, show the appearance of two doublets at δ 31.9 and 26.1
ppm with a 2JPP = 330 Hz, consistent with the formation of the intermediate A by substitution of one
PPh3 with PCy3 (Scheme 1).

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DOI: 10.1039/C9DT02616A
CO
Cl
H2N
Cl
Ru PCy3
NH2
1
H2N
NH2
NH2
N
CO
CO
CO
Cl
Cl
Cl
PR3
Ph3P Ru PR3
Ph3P Ru PPh3
N
Ru PCy3
Cl
Cl
Cl
dmf
dmf
NH2
A
2
H2N
R = Cy, iPr
NH2
CO
Cl
H2N
Cl
Ru PiPr3
NH2
3
Scheme 1. Synthesis of trans-[RuCl2(CO)(PR3)(NN)] (1-3).
Similarly to 1, the derivative trans-[RuCl2(CO)(PCy3)(ampy)] (2) has been prepared by reaction
of [RuCl2(CO)(dmf)(PPh3)2] with PCy3 and ampy52 (84% yield), while trans-[RuCl2(CO)(PiPr3)(en)]
(3) has been obtained from the ruthenium precursor using PiPr3 and en in CH2Cl2 at RT (66% yield)
31
(Scheme 1). The P{1H} NMR spectrum of 2 in CD2Cl2 displays a singlet at δ 56.9 ppm, a value
very close to that of 1 (δ 55.6 ppm). In the 1H NMR spectrum of 2 the methylene and the NH2 protons
of ampy appear as two triplets at δ 4.71 and 4.19 ppm, with 3JHH = 6.0 Hz, respectively. The 13C{1H}
NMR signal of the carbonyl group is observed as a doublet at δ 207.6 ppm (d, 2JCP = 17.8 Hz), while
the CO stretching band in the IR spectrum is at 1941 cm-1, values close to those of 1. Complex 3
shows spectroscopic data related to those of 1 and 2 with an IR CO stretching absorbance at 1921 cm-
1. Treatment of the acetate precursor [Ru(OAc)2(CO)(PPh3)2] with en in methanol at 70 °C for 2 h,
affords the cationic complex [Ru(OAc)(CO)(PPh3)(en)]OAc (4), isolated in 73% yield (Scheme 2).

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DO+I:O10A.1c03V9ie/wC9ADrtiTcl0e2O6n1l6inAe
CO
O
O
Ru PPh3
H2N
NH2
CO
CO
Ru
O
OAc
OAc
PPh3
N
N
4
N
Ru
N
PPh3
Ph3P
- PPh3
AcO
O
+ OAc
CO
O
B, B'
O
N
Ru PPh3
NH2
5
N
N =
H2N
NH2 H2N
N
Scheme 2. Synthesis of [Ru(OAc)(CO)(PPh3)(NN)]OAc (NN = en 4, ampy 5) complexes.
The 31P{1H} NMR spectrum of 4 in CD2Cl2 shows a singlet at δ 47.3 ppm. The en NH protons
give four broad signals at δ 6.97, 5.22, 3.13 and 2.66 ppm in the 1H NMR spectrum, consistent with
the presence of an N-H. . .O hydrogen bond interaction, whereas the acetate methyl groups afford two
13
singlets at δ 1.98 and 1.58 ppm. In the C{1H} NMR spectrum, the CO appears as a doublet at δ
204.9 ppm ( 2JCP = 18.4 Hz), whereas the CH2N appear as doublets at δ 46.7 and 43.9 ppm. The two
acetates afford the signals at δ 181.4 and 179.3 ppm for the COMe and at δ 25.2 and 24.3 ppm for the
CH3 corresponding moieties, while the IR νCO adsorption band of the CO is at 1924 cm-1. Control
experiments show that reaction of [Ru(OAc)2(CO)(PPh3)2] with en in dichloromethane at RT (30
min), leads to the formation of 4 and trans-[Ru(OAc)2(CO)(PPh3)(en)] (B) (δP 51.6 ppm) in about
2/3 molar ratio. The 1H NMR spectrum of B shows triplets at δ 4.95 and 3.90 ppm attributable to the
NH2CH2 moiety, respectively, and a singlet at δ 1.62 ppm for the acetate ligand (see ESI, Figures S13
and S14). By refluxing this mixture in methanol for 12 h, complete conversion to 4 is achieved, thus
indicating that upon trans to cis isomerization the thermodynamically most stable complex displays
a
bidentate acetate, while the second acetate acts as the counterion. Similarly,
[Ru(OAc)(CO)(PPh3)(ampy)]OAc (5) has been obtained by reaction of [Ru(OAc)2(CO)(PPh3)2] with
ampy in methanol at reflux for 6 h (Scheme 2). The 31P{1H} NMR spectrum reveals a signal at δ 49.8
ppm, while the ampy NH protons give two signals at δ 8.87 and 1.27 ppm in the 1H NMR spectrum
indicating a N-H. . .O hydrogen bond interaction. In the 13C{1H} NMR spectrum the CO appears as a
doublet at δ 205.7 ppm ( 2JCP = 17.9 Hz), whereas the two acetate groups give two resonances at δ
182.0 and 177.7 ppm for the COMe and δ 25.0 and 24.2 for the CH3 moieties, likewise to 4. Finally,
the IR stretching bands of CO is at 1923 cm-1. Addition of sodium acetate (0.5 and 3.5 eq.) to 5 in

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CD3OD shows a progressive increase of the signal at δ 1.98 ppm for CH3CO2 , confirming that one
acetate of 5 is not coordinated to ruthenium (see ESI, Fig. S18).
As for 4, the intermediate species trans-[Ru(OAc)2(CO)(PPh3)(ampy)] (B’) was observed in
dichloromethane (δP 53.8 ppm) which converts quantitatively into 5 in refluxing methanol (see ESI,
Figures S19 and S20). Thus, we have demonstrated that the monocarbonyl ruthenium precursors
[RuCl2(CO)(dmf)(PPh3)2] and [Ru(OAc)2(CO)(PPh3)2] react with a monodentate phosphine and / or
a bidentate NN ligands affording the derivatives trans-[RuX2(CO)(PR3)(NN)] (X = Cl, OAc). While
the chloride derivatives are stable in solution, the acetate compounds undergo easily isomerization in
alcohol media, with the formation of the cationic [Ru(OAc)(CO)(PPh3)(NN)]OAc species in which
one acetate acts as bidentate ligand while the other is present as counterion.
Table 1. Selected spectroscopic data of the complexes 1-20 recorded at 20 °C
13C{1H}
31P{1H}
(Ru-CO)
νCO
Complex
δP
2JPP
(Hz)
δC
(ppm)
2JCP
(Hz)
(cm-1)a
(ppm)
trans-[RuCl2(CO)(en)(PCy3)] (1)
trans-[RuCl2(CO)(ampy)(PCy3)] (2)
trans-[RuCl2(CO)(PiPr3)(en)] (3)
55.6 (s)
-
-
-
-
206.0 (d) 16.8
207.6 (d) 17.8
205.8 (d) 17.0
204.9 (d) 18.4
1936
1941
1921
1924
56.9 (s)
55.9 (s)
47.3 (s)
[Ru(OAc)(CO)(PPh3)(en)]OAc (4)
[Ru(OAc)(CO)(PPh3)(ampy)]OAc
(5)
49.8 (s)
-
205.7 (d) 17.9
1923
27.5 (t; 1P)
16.4-14.8 (m; 2P)
53.8 (m; 1P)
11.9
200.1 (dt)
3.0
trans-[RuCl2(CO)(dppb)(PPh3)] (6)
trans-[RuCl2(CO)(dppf)(PPh3)] (7)
25.8
-
1974
1979
199.7 (br
16.0
46.4 (m; 2P)
t)
31.2 (pseudo-t; 1P) 24.3
25.8 (dd; 1P) 348.7
25.2
trans-[RuCl2(CO)((R)-
BINAP)(PPh3)] (8)
83.6
199.9 (dt)
15.8
1981
21.3 (dd; 1P) 348.6
23.3
47.7 (pseudo-t; 1P) 23.0
14.3 (dd; 1P) 357.2
23.0
trans-[RuCl2(CO)((R,Sp)-
Josiphos)(PPh3)] (9)
197.1 (m)
-
-
-
1979
1976
12.0 (dd; 1P)
357.2
22.7
trans-[RuCl2(CO)((R,R)-
Skewphos)(PPh3)] (10)
several multiplets
-

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48.0 (d)b
46.2 (d)b
major isomer
49.8 (d)c
45.4 (d)c
major isomer
49.6 (d)d
40.1 (d)d
major isomer
54.3 (d)d
48.8 (d)d
major isomer
37.4 (s)
21.6
15.8
[Ru(OAc)2(CO)(dppb)] (11)
[Ru(OAc)2(CO)(dppf)] (12)
26.4
30.4
27.6
38.8
204.5 (dd)b
1954
1974
1975
1958
203.3 (t)c 16.9
[Ru(OAc)2(CO)((R)-BINAP)] (13)
205.0 (t)d 27.2
201.8 (t)d
[Ru(OAc)2(CO)((R,R)-Skewphos)]
(14)
major
isomer
16.9
[RuCl(CO)(dppb)(en)]Cl (15)
[RuCl(CO)(dppf)(en)]Cl (16)
[Ru(OAc)(CO)(dppb)(en)]OAc (17)
[Ru(OAc)(CO)(dppb)(ampy)]OAc
(18)
-
-
-
199.5 (t) 13.6
199.9 (t) 14.4
203.9 (t) 14.8
1969
1960
1939
39.8 (s)
37.1 (s)
46.4 (d)
34.0 (d)
40.1 (s)
51.2 (d)
28.8
-
203.2 (t) 12.7
203.2 (t) 15.1
210.3 (t) 16.4
1944
1963
1959
[Ru(OAc)(CO)(dppf)(en)]OAc (19)
[Ru(OAc)(CO)(dppf)(ampy)]OAc
(20)
29.1
40.5 (d)
a nujol mull; b at - 80 °C; c at - 70 °C; d at - 60 °C.
Synthesis of monocarbonyl ruthenium chloride and acetate complexes with PP ligands.
The monocarbonyl diphosphine derivatives [RuCl2(CO)(PP)(PPh3)] and [Ru(OAc)2(CO)(PP)] are
easily obtained by reaction of the precursors [RuCl2(CO)(dmf)(PPh3)2] and [Ru(OAc)2(CO)(PPh3)2],
respectively, with a suitable (chiral) diphosphine. Treatment of [RuCl2(CO)(dmf)(PPh3)2] with dppb
in chloroform at 60 °C overnight gives trans-[RuCl2(CO)(dppb)(PPh3)] (6), which was isolated in
75% yield (Scheme 3).
CO
CO
Cl
Cl
P
P
dmf
+ PPh3 +
+
Ph3P Ru PPh3
P
Ru PPh3
Cl
Cl
dmf
P
PPh2
PPh2
PPh2
PPh2
PPh2
PPh2
PPh2
PPh2
PPh2
PPh2
P
P
=
Fe
Fe
10
6
7
8
9
Scheme 3. Synthesis of trans-[RuCl2(CO)(PP)(PPh3)] (6-10).

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31
The P{1H} NMR spectrum of 6 in CD2Cl2 at 20 °C exhibits a second-order ABX splitting
pattern with a triplet at δ 27.5 ppm (2JPP = 25.8 Hz) for one P atom of dppb and a broad multiplet in
the range of δ 16.4-14.8 ppm for PPh3 and one P atom of the dppb ligand.63 The NMR spectra of 6
show broad signals for the dppb methylene protons (δH 3.3-1.5 ppm) and a resonance at δC 200.1 ppm
for the CO, whereas the IR CO stretching absorption is at 1974 cm-1. Reaction of
[RuCl2(CO)(dmf)(PPh3)2] with the robust dppf52, 64 in toluene at reflux for 2 h affords trans-
[RuCl2(CO)(dppf)(PPh3)] (7), isolated in 39% yield (Scheme 3). This synthesis required higher
temperature with respect to that for 6, possibly due to the higher rigidity and the less basicity of dppf,
compared to dppb. Complex 7 displays two resonances at δP 53.8 and 46.4 ppm in a 1:2 ratio, with a
carbonyl signal at δC 199.7 ppm while the IR νCO band appears at 1979 cm-1. Similarly to 6, treatment
of [RuCl2(CO)(dmf)(PPh3)2] with one equivalent of the chiral (R)-BINAP52 in toluene at reflux for 2
h leads to trans-[RuCl2(CO)((R)-BINAP)(PPh3)] (8), isolated in 88% yield as a single stereoisomer
31
(Scheme 3). The P{1H} NMR spectrum of 8 in C7D8 displays an ABX pattern at 293 K, with a
pseudo-triplet at δ 31.2 ppm and two doublets of doublets at δ 25.8 and 21.3 ppm, respectively. The
upfield signals present a large coupling constant (2JPP = 348.7 Hz) for a PPh3 and a (R)-BINAP
phosphorus atoms in trans configuration. The CO ligand gives a doublet of triplets at δC 199.9 ppm
with a (2JCP)trans of 83.6 Hz and a (2JCP)cis of 15.8 Hz, in agreement with a planar arrangement of the
three P atoms and the CO ligand. Finally, the monocarbonyl derivatives trans-[RuCl2(CO)((R,Sp)-
Josiphos)(PPh3)] (9) and trans-[RuCl2(CO)((R,R)-Skewphos)(PPh3)] (10) are obtained by treatment
of [RuCl2(CO)(dmf)(PPh3)2] with the corresponding chiral diphosphine in toluene at reflux for 2 h,
and isolated in 65 and 87% yield, respectively (Scheme 3). While the (R,Sp)-Josiphos52 compound 9
was obtained as a single stereoisomer, the (R,R)-Skewphos52 complex 10 consists of a mixture of two
different stereoisomers, as inferred from 1H and 31P{1H} NMR measurements.
Treatment of [Ru(OAc)2(CO)(PPh3)2] with dppb in CH2Cl2 overnight at RT, affords the
diacetate ruthenium monocarbonyl [Ru(OAc)2(CO)(dppb)] (11), isolated in 88% yield, by
displacement of both PPh3 ligands (Scheme 4).

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O
O
CO
CO
O
O
P
P
P
Ru
O
+
+
2 PPh3
Ru PPh3
O
Ph3P
O
P
O
PPh2
P
P
PPh2
PPh2
PPh2
PPh2
PPh2
=
Fe
PPh2
PPh2
12
13
14
11
Scheme 4. Synthesis of [Ru(OAc)2(CO)(PP)] (11-14).
The 31P{1H} NMR spectrum of 11 in CD2Cl2 at RT displays a broad signal at δ 46.8 ppm , while
upon cooling two doublets at δ 48.0 and 46.2 ppm with 2JPP = 26.4 Hz and two broad signals in the
range δ 45.2-34.0 ppm appear at 193 K, indicating the presence of two species in about 3:1 ratio (see
ESI, Fig. S38). The 1H and 13C{1H} NMR spectra for the methyl groups at RT show broad singlets
at δH 1.42 and δC 23.7 ppm, respectively, whereas at low temperature the spectra reveal the presence
31
of two species, in agreement with the P{1H} NMR data, with an IR CO stretching band at 1954
cm-1. The fluxionality of 11 is likely due to the rapid intramolecular exchange of the monodentate
and bidentate acetate groups, a well-known behavior observed for the analogous trifluoroacetate
[Ru(CF3CO2)2(CO)(PPh3)2].37, 38, 65 It is likely that the presence of different species at low temperature
is due to the different coordination modes of the acetate groups and the conformers of the diphosphine
ligand. The complex [Ru(OAc)2(CO)(dppf)] (12) is easily obtained by reaction of
[Ru(OAc)2(CO)(PPh3)2] with dppf in toluene at reflux for 2 h and isolated in 67% yield (Scheme 4).
At RT the 31P{1H} NMR spectrum of 12 in CD2Cl2 shows a broad singlet at δ 50.7 ppm, while upon
cooling at 203 K three species appear (7:2:1 ratio), with the major isomer displaying two doublets at
δ 49.8 and 45.4 ppm with 2JPP of 30.4 Hz. In the 1H NMR spectrum, the broad signal at δ 1.56 ppm
is for the two acetates, while at low temperature three isomers containing two non-equivalent acetates
31
(δ 1.73-1.33 ppm) are observed, in agreement with the P{1H} measurements (see ESI, Fig. S45).
The IR νCO of 12 is at 1974 cm-1, shifted at higher wavenumber compared to 11 and
[Ru(OAc)2(CO)(dippf)]52, 66 (1939 cm-1), due to the low basicity of dppf.67-71 Similarly to 12, the
chiral complexes 13 and 14 are obtained from [Ru(OAc)2(CO)(PPh3)2] and the suitable diphosphine,
namely (R)-BINAP and (R,R)-Skewphos, in toluene at reflux and isolated in good yield (71-93%,
31
1
Scheme 4). P{1H} and H NMR spectra of 13-14 display at RT broad peaks due to the fluxional

Dalton Transactions
Page 10 of 33
10
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behavior of these complexes, whereas at low temperature several isomers appear in thDeONI: 1M0.1R039s/pC9eDcTt0r2a616A
(see ESI, Fig. S50-S59). Thus, by difference to the monocarbonyl ruthenium diphosphine complexes
with chloride ligands, the corresponding acetate derivatives do not contain an additional PPh3, on
account of the ability of the carboxylate to act as bidentate ligand.
Synthesis of the monocarbonyl ruthenium chloride and acetate complexes with NN and PP
ligands. The ruthenium complexes [RuX(CO)(PP)(NN)]X (X = Cl, OAc) can be obtained by
reactions of the precursors [RuX2(CO)(dmf)n(PPh3)2] (X = Cl, n = 1; X = OAc, n = 0),
[RuCl2(CO)2]n72 and the above reported derivatives [RuX2(CO)(PP)(PPh3)n] (X = Cl, n = 1; X = OAc,
n = 0) with PP and / or NN ligands. Treatment of [RuCl2(CO)(dmf)(PPh3)2] with dppb in CH2Cl2,
followed by addition of en at RT, leads to the cationic derivative [RuCl(CO)(dppb)(en)]Cl (15)
isolated in 87% yield (Scheme 5).
CO
Cl
P
Ph3P Ru PPh3
H2N NH2
CH2Cl2
+
P
Cl
dmf
CO H2
N
Cl
H2N NH2
iPrOH
P
P
P
[RuCl2(CO)2]n
Ru
N
+
P
H2
Cl
15, 16
CD2Cl2
CO
Cl
P
Ru PPh3
+
PPh2
P
P
H2N NH2
PPh2
PPh2
=
Fe
Cl
PPh2
P
16
15
6, 7
Scheme 5. Synthesis of the cationic [RuCl(CO)(PP)(en)]Cl complexes 15 and 16.
Alternatively, 15 can be prepared in a more advantageous way (93% yield) by reaction of
[RuCl2(CO)2]n with dppb in 2-propanol, followed by treatment with en at reflux for 2 h via
decarbonylation (Scheme 5). The 31P{1H} NMR spectrum of 15 in CD2Cl2 displays a singlet at δ 37.4
ppm, whereas the 13C{1H} NMR measurements give a triplet at δ 199.5 ppm (2JCP = 13.6 Hz) for the
CO and a singlet at δ 45.9 ppm for the en ligand. The IR CO stretching absorbance of 15 appears at
1969 cm-1.53 Employment of dppf with [RuCl2(CO)(dmf)(PPh3)2] affords the complex

Page 11 of 33
Dalton Transactions
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[RuCl(CO)(dppf)(en)]Cl (16) which is isolated in 88% yield. Complexes 16 shows similar
DOI: 10.1039/C9DT02616A
spectroscopic data observed for 15, with a 31P{1H} NMR singlet at δ 39.8 ppm and IR νCO at 1960
cm-1. In addition, complexes 15 and 16 are quantitatively formed by reaction of 6 and 7 with en at RT
(2 h), as inferred from NMR measurements in CD2Cl2 (Scheme 5).
The acetate complex [Ru(OAc)(CO)(dppb)(en)]OAc (17) is obtained through a one-pot reaction
from [Ru(OAc)2(CO)(PPh3)2], dppb and en in CH2Cl2 and isolated in 97% yield (Scheme 6).
O
CO
O
N
N
P
P
Ru PPh3
Ph3P
+
O
O
CO
Ru
OAc
N
N
P
P
OAc
O
CO
17-20
O
N
P
Ru
O
+
O
N
P
PPh2
PPh2
PPh2
PPh2
11, 12
Fe
H2N
NH2
17
18
19
20
H2N
N
Scheme 6. Synthesis of the acetate complexes [Ru(OAc)(CO)(PP)(NN)]OAc.
Likewise the analogous chloride complex 15, the acetate derivative 17 displays in the 31P{1H}
NMR spectrum (CD3OD) one singlet at δ 37.1 ppm, while the CO gives a triplet at δC 203.8 ppm
(2JCP = 14.8 Hz). The doublet at δ 46.6 ppm (3JCP = 11.0 Hz) and the singlet at δ 44.9 ppm are ascribed
to the en CH2 moieties, whereas the two acetate ligands display the signals at δ 182.8 and 182.5 ppm
for the COMe and at δ 25.7 and 24.1 ppm for the methyl groups. Interestingly, the 1H NMR spectrum
of 17 exhibits four different N-H protons, with one NH2 group showing a signal at δ 7.27 ppm,
suggesting an NH···O hydrogen bond interaction with one acetate,62 and the other at δ 1.24 ppm, as
inferred from 15N-1H HSQC 2D NMR analysis (see ESI, Fig. S69), while the infrared stretching band
at 1939 cm-1 is for CO ligand. Conversely, 17 can also be obtained from 11 and en in CD2Cl2 at RT.
Reaction of 11 with ampy in toluene at RT (30 min) leads to the cationic complex

Dalton Transactions
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[Ru(OAc)(CO)(dppb)(ampy)]OAc (18), isolated in 87% yield (Scheme 6). 31P{1H} NMR spectrum
DOI: 10.1039/C9DT02616A
2
of 18 in C7D8 displays two doublets at δ 46.4 and 34.0 ppm with a JPP = 28.8 Hz, whereas the
diastereotopic methylene protons of the ampy give in the 1H NMR spectrum two signals at δ 4.22 and
2
3
15
3.21 ppm with JHH = 12.4 Hz and JHH = 10.2 and 10.7 Hz. The N-1H HSQC 2D NMR analysis
reveals that the NH2 signals are at δ 6.21 and 1.67 ppm, which is consistent with the presence of a
NH···O hydrogen bond interaction, as observed for 17. The 13C{1H} NMR signal of CO is a triplet
at δ 203.2 ppm with 2JCP = 16.7 Hz, while the IR νCO is at 1944 cm-1, similarly to en derivative 17.
Complex [Ru(OAc)(CO)(dppf)(en)]OAc (19) was synthesized from 12 by reaction with en in toluene
and isolated in 88% yield (Scheme 6). Complex 19 shows similar spectroscopic data observed for 17,
with the 31P{1H} NMR singlet at δ 40.1 ppm in CD2Cl2, whereas the 13C{1H} NMR CO signal appears
as a triplet at δ 203.2 ppm ( 2JCP = 15.1 Hz). The acetate carbonyl resonances appear as a singlet at δ
181.4 ppm for the free acetate, and a doublet of doublets at δ 176.6 ppm (3JCP = 12.1 Hz, 3JCP = 5.6
Hz) for the coordinated ligand. Finally, the IR spectra of 19 exhibits a νCO band at 1963 cm-1, whereas
the stretching bands at 1617 and 1569 cm-1 can be attributed to the acetate groups. In addition,
treatment of 12 with ampy in toluene at RT leads to [Ru(OAc)(CO)(dppf)(ampy)]OAc (20), which
has been isolated in 87% yield (Scheme 6). The spectroscopic data of 20 resembles that of the
1
analogue ampy derivative 18, with the two H NMR signals at δ 4.84 and 2.55 ppm for the
diastereotopic CH2N protons, whereas the NH2 resonances are found at δ 6.07, and 2.33 ppm. The
31P{1H} NMR spectrum of 20 displays two doublets at δ 51.2 and 40.5 ppm with a 2JPP = 29.1 Hz,
whereas the 13C{1H} NMR CO signal is a triplet at δ 210.3 ppm (2JCP = 16.4 Hz); the IR CO stretching
band is at 1959 cm-1. Thus, according to procedure a series of PP and NN monocarbonyl complexes
with different stereoelectronic properties bearing chloride and acetate ligands have been easily
isolated and characterized.
Reduction of aldehydes and ketones via TH and HY catalyzed by monocarbonyl
ruthenium complexes. The catalytic activity of the monocarbonyl ruthenium complexes has been
investigated in the reduction of acetophenone a via both TH, with 2-propanol in the presence of
NaOiPr and HY with H2 (30 bar) in ethanol with KOtBu (Scheme 7). The in situ addition of NN
ligands to the ruthenium phosphine derivatives has proven to accelerate the catalytic reactions.
Complexes 1, 2 and 3 (S/C = 1000), bearing the en and ampy ligands in combination with the strongly
coordinating alkyl monophosphine PCy3 or PiPr3, display poor activity in the TH of a (27-54% conv.),
in 2-propanol at reflux after 60-90 min (Table 2, entries 1-3). A higher activity is observed for the
cationic acetate derivatives 4 and 5 in the presence of the less basic PPh3, (81 and 95% conv.,
respectively) after 90 min (entries 4-5). The results obtained with 1-5 are in agreement with the higher

Page 13 of 33
Dalton Transactions
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trans influence73, 74 of PPh3 vs Cl, allowing a shorter induction time for the foDrmOI:a1t0i.o10n39/oCf9DTth02e616A
catalytically active Ru hydride species. The complexes [RuCl2(CO)(PP)(PPh3)] (PP = dppb, 6; PP =
dppf, 7) show poor activity (10% in 120 min and 98% in 48 h), while the addition of ampy and
displacement of PPh3 (vide infra) leads to an increase of activity, as observed for 7 (90% conv.; entries
6-8). Employment of the chiral (R)-BINAP complex 8 in the presence of (R,R)-DPEN52 affords high
conversion (97%) with TOF of 8400 h-1, respectively, but accompanied by poor ee (entry 9). The rate
of the TH of a with the (R,Sp)-Josiphos derivative 9 is low and increases by addition of (R,R)-DPEN,
(S)-1-phenylethanol is obtained in 59% ee (entries 10-11).
TH
2-propanol, T = 82 °C
2 mol% NaOiPr
O
OH
R'
1 16 18
catalysts
-
,
R
R'
R
HY
H2, T = 70 °C
2 mol% KOtBu
O
O
O
O
O
MeO
O2N
Cl
a
c
d
b
e
O
O
O
HO
O
O
O
i
f
g
h
Scheme 7. Reduction of carbonyl compounds via TH and HY, catalyzed by complexes 1-16, 18.
Complex 10 bearing the (R,R)-Skewphos in combination with (±)-iPr-ampy52 affords the (R) alcohol
with 67% ee (TOF = 5800 h-1) (entry 12). The acetate dppb 11 and dppf 12 derivatives are poorly
active and the in situ addition of ampy leads to 93 and 72% conversion in 2 h, respectively, with TOF
7400 and 6900 h-1, showing a faster rate compared to their corresponding chlorides 6 and 7
complexes, which require displacement of a PPh3 by the NN ligand (entries 13-15). With the (R)-
BINAP 13 and (R,R)-Skewphos 14 complexes in combination with ampy, (±)-iPr-ampy and (R,R)-

Dalton Transactions
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DPEN a considerable increase of the reaction rate is observed, with 90-97% conversion in 5-30 min
DOI: 10.1039/C9DT02616A
(TOF = 10000-18000 h-1), but low enantioselectivity has been attained (up to 39%) (entries 16-20).
Finally, the dppb and dppf complexes 15, 16 and 18 bearing en and ampy afford the TH of a with
better performances with respect to those observed with the in situ reactions of 6, 7, 11 with the
nitrogen ligands (entries 21-23).
Table 2. Catalytic TH of acetophenone (0.1 M) with complexes 1-16, 18 (S/C = 1000) and NaOiPr
(2 mol%) in 2-propanol at 82 °C.
Ligand
(5 equiv.)
Conv.[a] TOF[b] e.e.
Entry
Complex
Time [min]
[%]
54
42
27
81
95
10
38
90
94
97
96
95
31
93
72
95
97
81
95
90
94
88
91
[h-1]
(%)
1
2
1
2
-
90
60
-
-
-
-
-
-
-
-
-
-
3
3
-
90
-
4
4
-
90
-
5
5
-
90
-
6
6
-
120
120
120
120
8 h
120
60
-
7
6
ampy
-
8
7
ampy
3500
-
9
8
(R,R)-DPEN
8400
180
32 (S)
5 (S)
59 (S)
67 (R)
-
10
11
12
13
14
15
16
17
18
19
20
21
22
23
9
-
9
(R,R)-DPEN
(±)-iPr-ampy[c]
1200
5800
-
10
11
11
12
13
13
14
14
14
15
16
18
-
120
120
120
5
ampy
7400
6900
18000
15000
6400
10000
15000
2100
3900
7100
-
ampy
-
ampy
23 (S)
30 (S)
25 (R)
25 (R)
39 (R)
-
(R,R)-DPEN
5
-
120
30
ampy
(±)-iPr-ampy[c]
5
-
-
-
90
90
-
90
-
a The conversion has been determined by GC analysis. b Turnover frequency (moles of ketone
converted to alcohol per mole of catalyst per hour) at 50% conversion. c 2 eq. with respect to the
diphosphine precursors.
The monocarbonyl derivatives have been investigated in the TH of ketones and aldehydes. Thus, the
ampy-derivative 5 (S/C = 1000) catalyzes the quantitative reduction of benzophenone f to benzhydrol

Page 15 of 33
Dalton Transactions
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in 0.5 h (Table 3, entry 1). Interestingly, complex 1 bearing en and PCy3 affords the TH of trans-
DOI: 10.1039/C9DT02616A
cinnamaldehyde g, furfural h and 5-(hydroxymethyl)furfural (5-HMF) i, which belong to the
lignocellulosic biomass platform aldehydes, in 16-60 h (entries 2-4). It is worth pointing out that
aldehydes are substrates that are not easily reduced on account of incoming side reactions, which may
lead to catalyst deactivation.75, 76 A higher activity has been observed with complex 18 bearing ampy
and dppb for g and h, affording 98 and 99% conversion after 12 and 1 h, respectively, and without
hydrogenation of C=C bond under these catalytic conditions (entries 5-6).
Table 3. Catalytic TH of aldehydes and ketones (0.1 M) to alcohols with complexes 1, 5 and 18
(S/C = 1000) and NaOiPr (2 mol%) as base in 2-propanol at 82 °C.
Entry
Complex
substrate Time [h] Conv.[a] [%]
1
2
3
4
5
6
5
1[b]
1
f
g
h
i
0.5
16
16
60
12
1
94
97
92
96
98
99
1
18[b]
g
h
18
aThe conversion has been determined by GC analysis.
bUsing K2CO3 5 mol% as base.
The catalytic results obtained with 1-18 indicate that the chloride and the acetate monocarbonyl
phosphine complexes without nitrogen ligands display poor activity in TH reactions and their
performances increase by addition of primary amine ligands, facilitating the formation of the
catalytically active Ru–H species.77, 78 NMR studies in solution show that reaction of 18 with NaOiPr
(2 equiv.) in 2-propanol at RT affords a monohydride species with the hydride ligand (δ - 5.58 ppm)
trans to a phosphorus atom ((2JHP)trans = 115.6 Hz and (2JHP)cis = 19.8 Hz), in agreement with the
results observed for [RuCl(CO)(dppp)(ampy)]Cl complex53 (see ESI, Fig. S73). The low
enantioselectivity observed for the BINAP 8 and 13 compounds, by difference to the Noyori trans-
[RuCl2(BINAP)(NN)] system,79, 80 it is possibly due to the formation of a trans H-Ru-P species.
The monocarbonyl amine complexes are also found active in the HY of a in ethanol at 70 °C
at 30 bar of H2 pressure. The HY reactions have been carried out both in a catalyst screening system
(8 vessels Endeavor™ Biotage system), that allows parallel reactions to be performed, and in a
stainless steel autoclave following the single process. The PCy3 and PiPr3 1-3 and the dppb 15
complexes (S/C = 2000) give full hydrogenation of a (2.0 M) within 16 h in the presence of KOtBu
(2 mol%) (Table 4, entries 1-4).

Dalton Transactions
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Table 4. Catalytic HY of acetophenone (a) (2.0 M) with complexes 1-3, 15 (S/C =D2O0I:0100.)10(339/0C9bDaT0r2)616A
of H2 and KOtBu (2 mol%) in EtOH at 70 °C.
Entry
Complex
Time [h] Conv.[a] [%]
1
2
3
4
1
2
16
16
16
16
99
99
98
99
3
15
a The conversion has been determined by GC analysis.
In addition, complexes 2 and 15 (S/C = 1000-10000) have been found active in the HY of several
ketones. 2'-Methylacetophenone b, 2'-choloracetophenone c and 4'-methoxyacetophenone d are
quantitatively reduced to the corresponding alcohols with 2, whereas 4'-nitroacetophenone e leads to
poor conversion (10%) (Table 5, entries 1-4). In the HY of c and f, complex 15 displays much of the
same activity of 2, affording complete conversion, while the reduction of d leads to 75% conversion
(Table 5, entries 5-8). Therefore, the monocarbonyl ruthenium complexes with a monophosphine or
a diphosphine in combination with en and ampy have proven to catalyze the ketone HY with high
productivity.
Table 5. Catalytic HY (30 bar) of ketones (2.0 M) to alcohols with complexes 2, 15 and KOtBu
(2 mol%) as base in EtOH at 70 °C.
Entry Complex Substrate
S/C
Time [h] Conv.[a] [%]
1
2
3
4
5
6
7
8
2
2
b
c
d
e
f
10000
10000
1000
16
16
5
99
99
99
10
98
98
75
99
2
2
10000
1000
16
5
2
15
15
15
c
d
f
10000
1000
16
5
1000
5
a The conversion has been determined by GC analysis.
Conclusions
In summary, we have described a general approach for the straightforward preparation of a series of
monocarbonyl ruthenium complexes, containing bidentate NN and/or PP ligands with chloride and
acetate, starting from the precursors [RuCl2(CO)(PPh3)2(dmf)] and [Ru(OAc)2(CO)(PPh3)2]. The

Page 17 of 33
Dalton Transactions
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acetate complexes show a fluxional behavior in solution on account of the tendency of the acetate to
DOI: 10.1039/C9DT02616A
switch from the mono to bidentate mode of coordination. The reported complexes containing the
Ru(CO)(P)(NN) and Ru(CO)(PP)(NN) motifs show good to high catalytic activity in the transfer
hydrogenation and hydrogenation of a number of carbonyl compounds. These results will be helpful
for the designing of novel monocarbonyl ruthenium complexes containing chelate ligands. Studies
are in progress to extend this protocol for the preparation of new derivatives with pincer ligands and
expand the use of ruthenium carbonyl complexes in catalytic C-H activation reactions.
Experimental
General
All reactions were carried out under an argon atmosphere using standard Schlenk techniques. Unless
stated otherwise, the solvents were carefully dried by standard methods and distilled under argon
before use. The ruthenium compounds [RuCl2(CO)(dmf)(PPh3)2],59 [RuCl2(CO)2]n,72 and
[Ru(OAc)2(CO)(PPh3)2]60 were prepared according to literature procedures, whereas all other
chemicals were purchased from Aldrich and Strem and used without further purification. NMR
measurements were recorded on a Bruker AC 200 and Avance III HD NMR 400 spectrometers.
Chemical shifts (ppm) are relative to TMS for 1H and 13C{1H}, whereas H3PO4 was used for 31P{1H}.
Elemental analyses (C, H, N) were carried out with a Carlo Erba 1106 analyzer, whereas GC analyses
were performed with a Varian CP-3380 gas chromatograph equipped with a 25 m length MEGADEX-
ETTBDMS-β chiral column with hydrogen (5 psi) as the carrier gas and flame ionization detector
(FID). The injector and detector temperature was 250 °C, with initial T = 95 °C ramped to 140 °C at
3 °C/min rate and then to 210 °C at 20 °C/min, for a total of 20 min of analysis.
Synthesis of trans-[RuCl2(CO)(PCy3)(en)] (1)
[RuCl2(CO)(dmf)(PPh3)2] (250 mg, 0.31 mmol) was suspended in dichloromethane (5 mL) and
reacted with PCy3 (175 mg, 0.62 mmol, 2 equiv.) stirring the mixture for 3 h at RT. En (25 μL, 0.37
mmol, 1.2 equiv) was added and the resulting solution was stirred for 3 h at RT. The solvent was
reduced to about half volume by evaporation under reduced pressure, and the addition of n-pentane
(5 mL) afforded the precipitation of the product. The solid was filtered, washed with diethyl ether
(2x10 mL) and dried under reduced pressure. Yield: 149 mg (89%). Elemental analysis calcd (%) for
1
C21H41Cl2N2OPRu (540.52): C 46.66, H 7.65, N 5.18; found: C 46.59, H 7.58, N 5.26. H NMR
(200.1 MHz, CD2Cl2, 20 °C): δ = 3.70 (pseudo-t, JHH = 5.0 Hz, 2H; NH2), 3.27 (m, 2H; NH2), 3.10

Dalton Transactions
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(m, 2H; CH2N), 2.93 (m, 2H; CH2N), 2.20 (dd, 3JHH = 23.4 Hz, 3JHH = 12.3 Hz, 3H; PDCOHI: 1)0,.120.319/4C-91D.T0028616A
ppm (m, 30H; CH2 (Cy)). 13C{1H}, NMR (50.3 MHz, CD2Cl2, 20 °C): δ = 206.0 (d, 2JCP = 16.8 Hz;
CO), 43.5 (d, 3JCP = 2.8 Hz; CH2N), 42.3 (d, 3JCP = 1.5 Hz; CH2N), 35.3 (d, 1JCP = 21.0 Hz; PCH),
29.7 (d, 3JCP = 1.3 Hz; PCHCH2CH2), 28.2 (d, 2JCP = 10.0 Hz; PCHCH2), 27.0 ppm (d, 4JCP = 1.0 Hz;
CH ). 31P{1H} NMR (81.0 MHz, CD Cl , 20 °C): δ = 55.6 ppm (s). IR (Nujol): = 1936 (s) (C≡O)
휈
2
2
2
cm-1.
Synthesis of trans-[RuCl2(CO)(PCy3)(ampy)] (2)
Complex 2 was prepared following the procedure used for 1, with ampy (39 µL, 0.38 mmol, 1.2
equiv.) in place of en. Yield: 153 mg (84%). Elemental analysis calcd (%) for C25H41Cl2N2OPRu
(588.56): C 51.02, H 7.02, N 4.76; found: C 51.06, H 7.10, N 4.67. 1H NMR (200.1 MHz, CD2Cl2,
20 °C): δ = 9.11 (d, 3JHH = 5.3 Hz, 1H; ortho-CH of C5H4N), 7.76 (m, 1 H; para-CH of C5H4N), 7.50-
7.28 (m, 2H; meta-CH of C5H4N), 4.71 (t, 3JHH = 6.0 Hz, 2H; CH2), 4.19 (t, 3JHH = 6.0 Hz, 2H; NH2),
3
4
13
2.34 (qt, JHH = 12.1 Hz, JHH = 2,5 Hz, 3H; PCH), 2.18-1.09 ppm (m, 30H; CH2 (Cy)). C{1H}
NMR (50.3 MHz, CD2Cl2, 20 °C): δ = 207.6 (d, 2JCP = 17.8 Hz; CO), 160.1 (s; NCCH2), 152.6 (d,
2JCP = 1.2 Hz; ortho-CH of C5H4N), 137.6 (s; para-CH of C5H4N), 124.5 (d, 4JCP = 2.3 Hz; meta-CH
of C5H4N), 121.7 (d, 4JCP = 1.8 Hz; meta-CH of C5H4N), 50.6 (d, 3JCP = 2.2 Hz; CH2N), 34.5 (d, 1JCP
= 21.1 Hz; PCH), 29.6 (d, 3JCP = 1.3 Hz; PCHCH2CH2), 28.1 (d, 2JCP = 10.0 Hz; PCHCH2), 27.0 ppm
(s, CH ). 31P{1H} NMR (81.0 MHz, CD Cl , 20 °C): δ = 56.9 ppm (s). IR (Nujol): = 1941 (s) (C≡O)
휈
2
2
2
cm-1.
Synthesis of trans-[RuCl2(CO)(PiPr3)(en)] (3)
Complex 3 was prepared following the procedure used for 1, with PiPr3 (77 µL, 0.40 mmol, 1.3
equiv.) in place of PCy3. Yield: 86 mg (66%). Elemental analysis calcd (%) for C12H29Cl2N2OPRu
(420.32): C 34.29, H 6.95, N 6.66; found: C 34.20, H 7.01, N 6.60. 1H NMR (200.1 MHz, CD2Cl2,
20 °C): δ = 3.62 (m, 2H; NH2), 3.31 (m, 2H; NH2), 3.09 (m, 2H; CH2N), 2.94 (m, 2H; CH2N), 2.52
(m, 3H; PCH(CH3)2), 1.33 ppm (dd, 3JHP = 13.1 Hz, 3JHH = 7.3 Hz, 18H; CH(CH3)2). 13C{1H} NMR
(50.3 MHz, CD2Cl2, 20 °C): δ = 205.8 (d, 2JCP = 17.0 Hz; CO), 43.5 (d, 3JCP = 2.9 Hz; CH2N), 42.2
3
1
2
(d, JCP = 1.5 Hz; CH2N), 25.1 (d, JCP = 22.3 Hz; PCH(CH3)2), 19.6 ppm (d, JCP = 0.7 Hz;
31
CH(CH ) ). P{1H} NMR (81.0 MHz, CD Cl , 20 °C): δ = 55.9 ppm (s). IR (Nujol): = 1921 (s)
휈
3 2
2
2
(C≡O) cm-1.

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DOI: 10.1039/C9DT02616A
Synthesis of [Ru(OAc)(CO)(PPh3)(en)]OAc (4)
[Ru(OAc)2(CO)(PPh3)2] (200 mg, 0.26 mmol) was suspended in methanol (5 mL) and reacted with
en (22.5 µl, 0.34 mmol, 1.3 equiv), stirring the mixture for 15 h at reflux. The solvent was removed
from the obtained solution by evaporation under reduced pressure. The residue was dissolved in
dichloromethane (2 mL) and the product was precipitated by addition of n-heptane (10 mL). The solid
was filtered, washed with diethyl ether (3x4 mL), and n-pentane (2x5 mL) and finally dried under
reduced pressure. Yield: 108 mg (73%). Elemental analysis calcd (%) for C25H29N2O5PRu (569.56):
C 52.72, H 5.13, N 4.92; found: C 52.80, H 5.07, N 4.94. 1H NMR (200.1 MHz, CD2Cl2, 20 °C): δ =
7.72 (m, 4H; aromatic protons), 7.62-7.30 (m, 11H; aromatic protons), 6.97 (m, 1H; NH2), 5.22 (m,
1H; NH2), 3.13 (m, 1H; NH2), 2.89 (m, 1H; NCH2), 2.81 (m, 1H; NCH2), 2.66 (m, 1H; NH2), 2.49
(m, 1H; NCH2), 2.53 (m, 1H; NCH2), 1.98 (s, 3H; CH3CO), 1.58 ppm (s, 3H; CH3CO). 13C{1H} NMR
(50.3 MHz, CD2Cl2, 20 °C): δ = 204.9 (d, 2JCP = 18.4 Hz; CO), 181.4 (s; CH3CO), 179.3 (s; CH3CO),
134.3-128.4 (aromatic carbon atoms), 46.7 (d, 3JCP = 3.1 Hz; NCH2), 44.3 (d, 3JCP = 2.3 Hz; NCH2),
31
25.2 (s; CH3CO), 24.3 ppm (s; CH3CO). P{1H} NMR (81.0 MHz, CD2Cl2, 20 °C): δ = 47.3 ppm
(s). IR (Nujol): = 1924 (s) (C≡O), 1582 (C=O) cm-1.
휈
Synthesis of [Ru(OAc)(CO)(PPh3)(ampy)]OAc (5)
Complex 5 was prepared following the procedure used for 4 employing ampy (35 µl, 0.34 mmol, 1.3
equiv.) in place of en. Yield: 106 mg (66%). Elemental analysis calcd (%) for C29H29N2O5PRu
(617.60): C 56.40, H 4.73, N 4.54; found: C 56.45, H 4.69, N 4.48. 1H NMR (200.1 MHz, CD2Cl2,
20 °C): δ = 8.87 (m, 1H; NH2), 8.54 (m, 1H; ortho-CH of C5H4N), 7.81 (td, 3JHH = 7.6 Hz, 3JHH = 1.6
Hz, 1H; para-CH of C5H4N), 7.77-7.67 (m, 5H; aromatic protons), 7.48-7.38 (m, 11H; aromatic
protons), 7.32 (d, 3JHH = 7.7 Hz, 1H; meta-CH of C5H4N), 4.09 (dd, 2JHH = 16.0 Hz, 3JHH = 5.0 Hz,
2
3
3
1H; NCH2), 3.87 (ddd, JHH = 16.0 Hz, JHH = 10.0 Hz, JHH = 5.0 Hz, 1H; NCH2), 2.02 (s, 3H;
CH3CO), 1.33 (s, 3H; CH3CO), 1.27 ppm (m, 1H; NH2). 13C{1H} NMR (50.3 MHz, CD2Cl2, 20 °C):
2
3
δ = 205.7 (d, JCP = 17.9 Hz; CO), 182.0 (s; CH3CO), 177.7 (s; CH3CO), 161.2 (d, JCP = 1.8 Hz;
NCCH2), 150.2 (s; ortho-CH of C5H4N), 138.4 (s; para-CH of C5H4N), 134.9-120.9 (m; aromatic
carbon atoms), 52.9 (d, 3JCP = 2.3 Hz; NCH2), 25.0 (s; CH3CO), 24.2 ppm (s; CH3CO). 31P{1H} NMR
(81.0 MHz, CD Cl , 20 °C): δ = 49.8 ppm (s). IR (Nujol): = 1923 (s) (C≡O), 1579 (C=O) cm-1.
휈
2
2

Dalton Transactions
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DOI: 10.1039/C9DT02616A
Synthesis of trans-[RuCl2(CO)(dppb)(PPh3)] (6)
[RuCl2(CO)(dmf)(PPh3)2] (104 mg, 0.13 mmol) was suspended in CHCl3 (5 mL) and reacted with
dppb (55.4 mg, 0.13 mmol, 1 equiv.) stirring the mixture at 60 °C overnight. The obtained solution
was concentrated to about 1 mL, and the complex precipitated by addition of n-heptane (10 mL). The
solid was filtered, washed with of n-heptane (3x4 mL), diethyl ether (3x3 mL) and dried under
reduced pressure. Yield: 87 mg (75%). Elemental analysis calcd (%) for C47H43Cl2OP3Ru (888.76):
C 63.52, H 4.88; found: C 63.56, H 4.94. 1H NMR (200.1 MHz, CD2Cl2, 20 °C): δ = 7.77 (m, 4H;
aromatic protons), 7.66-6.97 (m, 28H; aromatic protons), 6.82 (m, 3H; aromatic protons), 3.06 (m,
1H; CH2), 2.72-2.10 (m, 4H; CH2), 1.63 ppm (m, 3H; CH2). 13C{1H} NMR (50.3 MHz, CD2Cl2, 20
°C): δ = 200.1 (dt, 2JCP = 11.9 Hz, 2JCP = 3.0 Hz; CO), 139.5-125.3 (m; aromatic carbon atoms), 33.0
31
(m; PCH2), 30.6 (m; PCH2), 25.4 (br s; CH2), 22.2 ppm (br s; CH2). P{1H} NMR (81.0 MHz,
2
CD2Cl2, 20 °C): δ = 27.5 (t, JPP = 25.8 Hz, 1P), 16.4-14.8 ppm (m, 2P). IR (Nujol): = 1974 (s)
휈
(C≡O) cm-1.
Synthesis of trans-[RuCl2(CO)(dppf)(PPh3)] (7)
[RuCl2(CO)(dmf)(PPh3)2] (199 mg, 0.25 mmol) suspended in toluene (5 mL), was reacted with dppf
(139 mg, 0.25 mmol, 1 equiv.) stirring the mixture at 110 °C for 2 h. The obtained solution was
concentrated to about 1 mL, n-heptane (10 mL) was added and the suspension was stirred at room
temperature for 1 h. The precipitate was filtered, washed with n-heptane (3x4 mL), diethyl ether (3x3
mL) and dried under reduced pressure. Yield: 99 mg (39%). Elemental analysis calcd (%) for
1
C53H43Cl2FeOP3Ru (1016.67): C 62.61, H 4.26; found: C 62.65, H 4.33. H NMR (200.1 MHz,
CD2Cl2, 20 °C): δ = 7.88-7.07 (m, 35H; aromatic protons), 4.53 (br s, 2H; C5H4), 4.44 (br s, 2H;
C5H4), 4.30 (br s, 2H; C5H4), 4.16 ppm (br s, 2H; C5H4). 13C{1H} NMR (100.6 MHz, CD2Cl2, 20 °C):
2
1
δ = 199.7 (br t, JCP = 16.0 Hz; CO), 135.2-125.0 (m; aromatic carbon atoms), 78.6 (d, JCP = 56.0
1
2
Hz; ipso-C5H4), 77.2 (d, JCP = 60.6 Hz; ipso-C5H4), 76.6 (d, JCP = 9.3 Hz; CH of C5H4), 75.7 (d,
2
3
2JCP = 9.8 Hz; CH of C5H4), 75.6 (d, JCP = 11.0 Hz; CH of C5H4), 74.8 (d, JCP = 7.2 Hz; CH of
C5H4), 74.2 (d, 3JCP = 7.0 Hz; CH of C5H4), 72.6 (d, 3JCP = 6.0 Hz; CH of C5H4), 72.1 ppm (d, 3JCP
6.4 Hz; CH of C5H4). 31P{1H} NMR (81.0 MHz, CD2Cl2, 20 °C): δ = 53.8 (m; 1P), 46.4 (m; 2P). IR
(Nujol): = 1979 (s) (C≡O) cm-1.
=
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DOI: 10.1039/C9DT02616A
Synthesis of trans-[RuCl2(CO)((R)-BINAP)(PPh3)] (8)
Complex 8 was prepared following the procedure used for 7, with (R)-BINAP (156 mg, 0.25 mmol,
1 equiv.) in place of dppf. Yield: 239 mg (88%). Elemental analysis calcd (%) for C63H47Cl2OP3Ru
(1084.96): C 69.74, H 4.37; found: C 69.77, H 4.40. 1H NMR (400.1 MHz, C7D8, 20 °C): δ = 8.73 (t,
3JHH = 8.6 Hz, 1H; aromatic proton), 8.14 (t, 3JHH = 8.8 Hz, 1H; aromatic proton), 7.77-7.68 (m, 1H;
aromatic proton), 7.36-7.27 (m, 1H; aromatic proton), 7.24 (t, 3JHH = 8.8 Hz, 1H; aromatic proton),
7.13-6.93 (m, 20H; aromatic protons), 6.81-6.74 (m, 1H; aromatic proton), 6.70-6.63 (m, 2H;
aromatic protons), 6.60-6.53 (m, 1H; aromatic proton), 6.49-6.38 (m, 2H; aromatic protons), 6.27
ppm (t, 3JHH = 6.0 Hz, 1H; aromatic proton). 13C{1H} NMR (100.6 MHz, C7D8, 20 °C): δ = 199.9 (dt,
2
2JCP = 83.6 Hz, JCP = 15.8 Hz; CO), 138.3-124.2 ppm (m; aromatic carbon atoms). 31P{1H} NMR
(162.0 MHz, C7D8, 20 °C): δ = 31.2 (pseudo-t, 2JPP = 24.3 Hz, 1P; ArPPh2), 25.8 (dd, 2JPP = 348.7
Hz, 2JPP = 25.2 Hz, 1P; PPh3), 21.3 ppm (dd, 2JPP = 348.6 Hz, 2JPP = 23.3 Hz, 1P; ArPPh2). IR (Nujol):
= 1981 (s) (C≡O) cm-1.
휈
Synthesis of trans-[RuCl2(CO)((R,Sp)-Josiphos)(PPh3)] (9)
Complex 9 was prepared following the procedure used for 7, with (R,Sp)-Josiphos (146 mg, 0.25
mmol, 1 equiv.) in place of dppf. Yield: 227 mg (87%). Elemental analysis calcd (%) for
C55H47Cl2FeOP3Ru (1044.72): C 63.23, H 4.53; found: C 63.16, H 4.47. 1H NMR (200.1 MHz, C7D8,
20 °C): δ = 8.66 (br s, 2H; aromatic protons), 8.07 (m, 2H; aromatic protons), 7.73 (m, 4H; aromatic
protons), 7.32 (m, 3H; aromatic protons), 7.25-6.80 (m, 18H; aromatic protons), 6.74 (m, 4H;
aromatic protons), 6.38 (m, 1H; aromatic proton), 5.84 (m, 1H; aromatic proton), 3.96 (br s, 5H;
C5H5), 3.79 (br s, 1H; C5H3), 3.73 (br s, 1H; C5H3), 3.64 (br s, 1H; C5H3), 1.34 (m, 1H; CHCH3),
13
1.13-0.96 ppm (m, 3H; CHCH3). C{1H} NMR (100.6 MHz, C7D8, 20 °C): δ = 197.1 (m; CO),
1
3
142.8-124.2 (m; aromatic carbon atoms), 94.9 (dd, JCP = 18.7 Hz, JCP = 4.1 Hz; ipso-C5H3), 77.1
1
3
(dd, JCP = 40.4 Hz, JCP = 5.6; ipso-C5H3), 71.8 (s; C5H3), 71.6 (s; C5H3), 71.5 (s; C5H3), 69.7 (s;
C5H5), 37.2 (d, 1JCP = 21.3 Hz; PCHCH3), 13.8 ppm (d, 2JCP = 5.7 Hz; PCHCH3). 31P{1H} NMR (81.0
2
2
2
MHz, C7D8, 20 °C): δ = 47.7 (pseudo-t, JPP = 23.0 Hz; 1P), 14.3 (dd, JPP = 357.2 Hz, JPP = 23.0
Hz; 1P), 12.0 ppm (dd, 2J = 357.2 Hz, 2J = 22.7 Hz; 1P). IR (Nujol): = 1979 (s) (C≡O) cm-1;
휈
PP
PP

Dalton Transactions
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Synthesis of trans-[RuCl2(CO)((R,R)-Skewphos)(PPh3)] (10)
Complex 10 was prepared following the procedure used for 7, with (R,R)-Skewphos (110 mg, 0.25
mmol, 1 equiv.) in place of dppf. Yield: 147 mg (65%) as a mixture of two diastereoisomers.
Elemental analysis calcd (%) for C48H45Cl2OP3Ru (902.78): C 63.86, H 5.02; found: C 63.79, H 4.97.
1H NMR (200.1 MHz, CD2Cl2, 20 °C): δ = 8.48 (m, 1H; aromatic proton), 8.04 (m, 4H; aromatic
protons), 7.71-7.17 (m, 21H; aromatic protons), 7.15-6.92 (m, 8H; aromatic protons), 6.19 (m, 1H;
aromatic proton), 4.07-3.81 (m, 1H; CH2), 3.69-3.29 (m, 1H; CH2), 3.14-2.87 (m, 1H; CH2), 2.86-
3
3
2.60 (m, 1H; CH2), 2.34-1.66 (m, 2H; CHCH3), 1.16 (dd, JHP = 13.7 Hz, JHH = 7.2 Hz; CHCH3),
1.05 (dd, 3JHP = 11.7 Hz, 3JHH = 6.6 Hz; CHCH3), 0.68 (dd, 3JHP = 11.5 Hz, 3JHH = 6.4 Hz; CHCH3),
0.55 ppm (dd, 3JHP = 12.3 Hz, 3JHH = 7.2 Hz; CHCH3). 31P{1H} NMR (81.0 MHz, CD2Cl2, 20 °C): δ
= 28.6 (d, 2JPP = 29.3 Hz, 1P), 24.4 (d, 2JPP = 29.3 Hz, 2P), 22.6 (dd, 2JPP = 29.1 Hz, 2JPP = 20.9 Hz,
3P), 17.2 ppm (d, 2J = 20.4 Hz, 1P). IR (Nujol): = 1976 (s) (C≡O) cm-1.
휈
PP
Synthesis of [Ru(OAc)2(CO)(dppb)] (11)
[Ru(OAc)2(CO)(PPh3)2] (300 mg, 0.39 mmol) was suspended in CH2Cl2 (5 mL) and reacted with
dppb (166 mg, 0.39 mmol, 1 equiv.), stirring the mixture at RT overnight. The obtained solution was
concentrated to about 0.5 ml evaporating the solvent under reduced pressure. The complex was
precipitated by addition of n-heptane (10 mL), filtered, washed with n-heptane (3x4 mL) and diethyl
ether (3x3 mL), and finally dried under reduced pressure. Yield: 231 mg (88%) as mixture of two
isomers in a ratio of 3:1 at - 60 °C that interchanges at RT. Elemental analysis calcd (%) for
C33H34O5P2Ru (673.65): C 58.84, H 5.09; found: C 58.80, H 5.10. 1H NMR (200.1 MHz, CD2Cl2, 20
°C): δ = 7.85-7.23 (m, 20H; aromatic protons), 2.84 (m, 2H; PCH2), 2.45 (m, 2H; PCH2), 1.98-1.66
(m, 4H; CH2CH2), 1.42 ppm (s, 6H; CH3CO). 1H NMR (200.1 MHz, CD2Cl2, - 80 °C): δ = 8.05-7.74
(m, 3H; aromatic protons), 7.72-7.20 (m, 15H; aromatic protons), 7.03 (t, 3JHH = 8.3 Hz, 2H; aromatic
protons), 3.30-2.36 (m, 3H; CH2), 2.29-1.38 (m, 5H; CH2), 1.56 (s, 3H; CH3CO minor isomer), 1.42
(s, 3H; CH3CO minor isomer), 1.34 (s, 3H; CH3CO major isomer), 1.14 ppm (s, 3H; CH3CO major
13
isomer). C{1H} NMR (50.3 MHz, CD2Cl2, 20 °C): δ = 204.8 (m; CO), 135.1-128.6 (m; aromatic
carbon atoms), 30.3 (br s; CH2), 29.7 (br s; CH2), 23.7 (br s; CH3CO), 23.6 ppm (br s; CH2). 13C{1H}
NMR (50.3 MHz, CD2Cl2, - 80 °C): δ = 204.5 (dd, 2JCP = 21.6 Hz, 2JCP = 15.8 Hz; CO), 202.6 (t, 2JCP
3
3
= 17.0 Hz; CO), 189.1 (s; CH3CO), 182.4 (t, JCP = 38.5 Hz; CH3CO), 175.3 (d, JCP = 2.6 Hz;
1
1
CH3CO), 137.3-122.7 (m; aromatic carbon atoms), 29.9 (d, JCP = 35.3 Hz; PCH2), 27.7 (d, JCP
=
32.7 Hz; PCH2), 25.2 (br s; CH2), 24.4 (s; CH3CO), 21.9 (d, 4JCP = 4.3 Hz; CH3CO), 20.5 ppm (br s;

Page 23 of 33
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CH2). P{1H} NMR (81.0 MHz, CD2Cl2, 20 °C): δ = 46.8 ppm (br s). P{1H} NMR (81.0 MHz,
CD2Cl2, - 60 °C): δ = 48.2 (d, 2JPP = 27.0 Hz, major isomer), 46.1 (d, 2JPP = 27.0 Hz, major isomer),
43.3 ppm (br s, minor isomer). 31P{1H} NMR (81.0 MHz, CD2Cl2, - 80 °C): δ = 48.0 (d, 2JPP = 26.4
Hz, major isomer), 46.2 (d, 2JPP = 26.4 Hz, major isomer), 45.2-34.0 ppm (br m; minor isomer). IR
(Nujol): = 1954 (s) (C≡O), 1614 (s), 1571 (s) (C=O) cm-1.
휈
Synthesis of [Ru(OAc)2(CO)(dppf)] (12)
[Ru(OAc)2(CO)(PPh3)2] (200 mg, 0.26 mmol) suspended in toluene (5 mL), was added of dppf (144
mg, 0.26 mmol, 1 equiv.) and the mixture was stirred at reflux for 2 h. The resulting solution was
concentrated to about 1 mL evaporating the solvent under reduced pressure, and the complex was
precipitated by addition of n-heptane (10 mL). The solid was filtered, washed with n-heptane (3x4
mL) and diethyl ether (3x3 mL), and dried under reduced pressure. Yield: 140 mg (67%) as mixture
of 3 isomers in a 7:2:1 ratio at - 70 °C that interchanges at RT. Elemental analysis calcd (%) for
C39H34FeO5P2Ru (801.56): C 58.44, H 4.28; found: C 58.38, H 4.30. 1H NMR (200.1 MHz, CD2Cl2,
20 °C): δ = 7.91-7.11 (br m, 20 H; aromatic protons), 4.80-4.06 (br m, 8H; C5H4), 1.56 ppm (br s,
6H; CH3CO). 1H NMR (200.1 MHz, CD2Cl2, - 70 °C): δ = 7.94 (t, 3JHH = 9.0 Hz; aromatic protons),
7.74 (t, 3JHH = 8.6 Hz; aromatic protons), 7.63-7.23 (m, aromatic protons), 4.97-3.97 (m; C5H4), 1.73
(s; CH3CO major isomer), 1.61 (s; CH3CO major isomer), 1.46 (s; CH3CO), 1.38 (s; CH3CO), 1.33
ppm (s; CH3CO). 13C{1H} NMR (50.3 MHz, CD2Cl2, 20 °C): δ = 134.6-127.2 (m; aromatic carbon
2
4
atoms), 75.6 (dd, JCP = 37.0 Hz, JCP = 4.3 Hz; C5H4), 73.1 (br m; C5H4), 72.6 (br m; C5H4), 24.2
ppm (br s; CH3CO). 13C{1H} NMR (50.3 MHz, CD2Cl2, - 70 °C): δ = 203.3 (t, 2JCP = 16.9 Hz; CO),
188.9 (s; CH3CO), 182.8 (s; CH3CO major isomer), 182.0 (br s; CH3CO major isomer), 175.7 (s;
CH3CO), 135.0-126.1 (m; aromatic carbon atoms), 79.0-76.1 (m; ipso-C5H4), 76.0 (d, JCP = 5.4 Hz;
C5H4), 75.4 (d, JCP = 7.3 Hz; C5H4), 75.0 (d, JCP = 7.4 Hz; C5H4), 74.4 (d, JCP = 8.9 Hz; C5H4 major
isomer), 72.7 (d, JCP = 6.1 Hz; C5H4 major isomer), 71.8 (d, JCP = 5.4 Hz; C5H4), 71.1 (d, JCP = 5.4
4
Hz; C5H4), 25.4 (s; CH3CO major isomer), 24.5 (d, JCP = 4.8 Hz; CH3CO), 23.8 ppm (s; CH3CO
major isomer). 31P{1H} NMR (81.0 MHz, CD2Cl2, 20 °C): δ = 50.7 ppm (br s). 31P{1H} NMR (81.0
MHz, CD2Cl2, - 70 °C): δ = 53.1 (d, 2JPP = 26.8 Hz), 52.0 (d, 2JPP = 27.5 Hz), 50.4 (d, 2JPP = 27.5 Hz),
49.8 (d, 2JPP = 30.4 Hz; major isomer), 45.4 (d, 2JPP = 30.4 Hz; major isomer), 43.5 ppm (d, 2JPP =
26.8 Hz). IR (Nujol): = 1974 (s) (C≡O), 1613 (s), 1569 (s) (C=O) cm-1.
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Synthesis of [Ru(OAc)2(CO)((R)-BINAP)] (13)
Complex 13 was prepared following the procedure used for 12 employing (R)-BINAP (162 mg, 0.26
mmol, 1 equiv.) in place of dppf. Yield: 210 mg (93%) as mixture of a predominant species (60%)
and several other isomers at - 60 °C that interchanges at RT. Elemental analysis calcd (%) for
C49H38O5P2Ru (869.86): C 67.66, H 4.40; found: C 67.70, H 4.32. 1H NMR (200.1 MHz, CD2Cl2, 20
°C): δ = 7.90 (m, 2H; aromatic protons), 7.71-7.24 (m, 20H; aromatic protons), 7.23-6.97 (m, 2H;
aromatic protons), 6.87 (d, 3JHH = 8.4 Hz, 2H; aromatic protons), 6.79 (d, 3JHH = 6.6 Hz, 2H; aromatic
protons), 6.69 (d, 3JHH = 8.4 Hz, 2H; aromatic protons), 6.60 (d, 3JHH = 6.5 Hz, 2H; aromatic protons),
1
1.29 ppm (br s, 6H; CH3CO). H NMR (200.1 MHz, CD2Cl2, - 60 °C): δ = 8.02-5.94 (m, 32H;
aromatic protons), 1.91 (s, 3H; CH3CO major isomer), 1.19 ppm (s, 3H; CH3CO major isomer).
13C{1H} NMR (50.3 MHz, CD2Cl2, - 60 °C): δ = 205.0 (t, 2JCP = 27.2 Hz; CO), 189.1 (d, 3JCP = 3.6
Hz; CH3CO major isomer), 183.2 (s; CH3CO), 182.2 (s; CH3CO), 181.0 (s; CH3CO), 176.0 (d, 3JCP
= 4.3 Hz; CH3CO major isomer), 139.40-124.62 (m; aromatic carbon atoms), 25.9 (s; CH3CO), 24.5
4
4
(s; CH3CO major isomer), 23.8 (d, JCP = 7.3 Hz; CH3CO), 22.3 (d, JCP =7.4 Hz; CH3CO major
isomer), 21.1 ppm (s; CH3CO). 31P{1H} NMR (81.0 MHz, CD2Cl2, 20 °C): δ = 50.5 (d, 2JPP = 25.3
Hz), 43.4 ppm (br s). 31P{1H} NMR (81.0 MHz, CD2Cl2, - 60 °C): δ = 49.6 (d, 2JPP = 27.6 Hz; major
isomer), 40.1 ppm (d, 2J = 27.6 Hz; major isomer). IR (Nujol): = 1975 (s) (C≡O), 1616 (s), 1505
휈
PP
(s) (C=O) cm-1.
Synthesis of [Ru(OAc)2(CO)((R,R)-Skewphos)] (14)
Complex 14 was prepared following the procedure used for 12 employing (R,R)-Skewphos (115 mg,
0.26 mmol, 1 equiv.) in place of dppf. Yield: 127 mg (71%) as mixture of several isomers at - 60 °C
that interchanges at RT. Elemental analysis calcd (%) for C34H36O5P2Ru (687.67): C 59.38, H 5.28;
1
found: C 59.29, H 5.21. H NMR (200.1 MHz, CD2Cl2, 20 °C): δ = 7.77-7.47 (m, 13H; aromatic
protons), 7.46-7.33 (m, 3H; aromatic protons),7.32-7.08 (m, 4H; aromatic protons), 3.15 (m, 1H;
PCHCH3), 2.73 (m, 1H; PCHCH3), 2.37-2.01 (m, 1H; CHCH2), 1.99-1.68 (m, 1H; CHCH2), 1.58 (br
s, 6H; CH3CO), 1.01 (dd, 3JHP = 15.6 Hz, 3JHH = 7.5 Hz, 3H; CHCH3), 0.89 ppm (dd, 3JHP = 12.5 Hz,
3JHH = 7.0 Hz, 3H; CHCH3). 1H NMR (200.1 MHz, CD2Cl2, - 60 °C): δ = 9.46 (m; aromatic proton),
3
7.72 (t, J(H,H) = 9.2 Hz; aromatic proton), 7.65-7.20 (m; aromatic protons), 7.07 (m; aromatic
proton), 6.92 (t, 3JHH = 9.2 Hz; aromatic proton), 3.10 (m; PCHCH3), 2.83 (m; PCHCH3), 2.68 (m;
PCHCH3), 2.32-1.81 (m, 1H; CHCH2), 1.75 (br s; CH3CO), 1.66 (s; CH3CO), 1.56-1.46 (m, 1H;
CHCH2), 1.25 (br s; CH3CO), 0.90 (dd, 3JHP = 15.2 Hz, 3JHH = 6.6 Hz; CHCH3), 0.75 ppm (dd, 3JHP

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= 12.2 Hz, 3JHH = 6.4 Hz; CHCH3). 13C{1H} NMR (50.3 MHz, CD2Cl2, - 60 °C): δ = D2O0I3: 1.04.10(3m9/;C9CDOT0)2,616A
201.80 (t, 2JCP = 16.9 Hz; CO major isomer), 189.0 (s; CH3CO), 187.4 (s; CH3CO), 183.1 (s; CH3CO),
182.6 (s; CH3CO), 181.9 (s; CH3CO major isomer), 180.8 (s; CH3CO), 176.4 (s; CH3CO), 174.8 (s;
CH3CO), 136.8-122.4 (m; aromatic carbon atoms), 36.2 (br s; CHCH2), 35.5 (br s; CHCH2), 35.0 (br
s; CHCH2 major isomer), 34.5 (br s; CHCH2), 31.0 (d, 1JCP = 31.6 Hz; PCH), 30.0 (d, 1JCP = 35.0 Hz;
PCH major isomer), 25.2 (s; CH3CO major isomer), 24.9 (d, 4JCP = 2.1 Hz; CH3CO), 24.7 (s; CH3CO),
23.7 (s; CH3CO), 23.1 (d, 4JCP = 4.6 Hz; CH3CO), 21.7 (s; CH3CO), 21.0 (s; CH3CO), 18.3-17.7 (m;
PCH), 15.8 (s; CHCH3), 15.2 (s; CHCH3 major isomer), 15.0 (s; CHCH3), 14.7 ppm (s; CHCH3).
31P{1H} NMR (81.0 MHz, CD2Cl2,20 °C): δ = 55.0 (br s), 50.6 ppm (br s). 31P{1H} NMR (81.0 MHz,
CD2Cl2, - 60 °C): δ = 59.5 (d, 2JPP = 35.1 Hz), 58.6 (d, 2JPP = 33.8 Hz), 56.7 (d, 2JPP = 34.2 Hz), 54.3
(d, 2JPP = 38.8 Hz; major isomer), 52.3 (d, 2JPP = 38.7 Hz), 51.6 (d, 2JPP = 36.5 Hz), 48.8 (d, 2JPP =
38.8 Hz; major isomer), 48.1 (d, 2JPP = 34.6 Hz), 48.0 (d, 2JPP = 36.5 Hz), 47.0 (d, 2JPP = 28.2 Hz),
46.1 ppm (d, 2J = 33.8 Hz). IR (Nujol): = 1958 (s) (C≡O), 1568 (s) (C=O) cm-1.
휈
PP
Synthesis of [RuCl(CO)(dppb)(en)]Cl (15)
Method A: [RuCl2(CO)(dmf)(PPh3)2] (200 mg, 0.25 mmol) was dissolved in CH2Cl2 (5 mL) and
reacted with dppb (124 mg, 0.29 mmol, 1.2 equiv.), stirring the mixture for 2 h at RT. En (25 µL,
0.37 mmol, 1.5 equiv) was then added and the slurry was stirred at RT for other 2 h. The resulting
solution was concentrated to about 0.5 mL by evaporation of the solvent under reduced pressure and
the complex was precipitated by addition of n-heptane (10 mL). The solid was filtered, washed with
diethyl ether (4x3 mL) and dried under reduced pressure. Yield: 149 mg (87%). Elemental analysis
calcd (%) for C31H36Cl2N2OP2Ru (686.56): C 54.23, H 5.29, N 4.08; found: C 54.18, H 5.22, N 4.10.
1H NMR (200.1 MHz, CDCl3, 20 °C): δ = 7.62-7.48 (m, 4H; aromatic protons), 7.44-7.35 (m, 16H;
aromatic protons), 4.94 (m, 2H; NH2), 3.60 (m, 2H; NH2), 2.96-2.38 (m, 4H; CH2 and CH2N), 2.35-
1.65 ppm (m, 8H; CH2 and CH2N). 13C{1H} NMR (50.3 MHz, CD2Cl2, 20 °C): δ = 199.5 (t, 2JCP
13.6 Hz; CO), 136.9-128.6 (aromatic carbon atoms), 45.9 (s; CH2N), 25.5 (t, 1JCP = 14.8 Hz; PCH2),
22.1 ppm (s; PCH CH ). 31P{1H} NMR (81.0 MHz, CD Cl , 20 °C): δ = 37.4 ppm (s). IR (Nujol):
=
휈
2
2
2
2
= 1969 (s) (C≡O) cm-1.
Method B: [RuCl2(CO)2]n (50 mg, 0.22 mmol) was suspended in 2-propanol (5 mL) and reacted with
dppb (94 mg, 0.22 mmol, 1 equiv.) stirring the mixture for 2 h at 90 °C. En (15 µL, 0.22 mmol, 1
equiv.) was added and the obtained solution was stirred for other 2 h at 90 °C, and then evaporated
under reduced pressure. The residue was dissolved in CHCl3 (3 mL) and stirred for 3 h at RT. The

Dalton Transactions
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volume was reduced by half, and the product was precipitated by addition of n-pentaDnOeI:(150.1m03L9/C).9DTTh02e616A
solid was filtered, washed with diethyl ether (2x10 mL) and dried under reduced pressure. Yield: 140
mg (93%).
Synthesis of [RuCl(CO)(dppf)(en)]Cl (16)
16
15
Complex was prepared following the procedure used for (method A) employing dppf (160 mg,
0.29 mmol, 1.2 equiv.) in place of dppb. Yield: 179 mg (88%). Elemental analysis calcd (%) for
C37H36Cl2FeN2OP2Ru (814.48): C 54.56, H 4.46, N 3.44; found: C 54.50, H 4.51, N 3.47. 1H NMR
(200.1 MHz, CD2Cl2, 20 °C): δ = 7.80-7.35 (m, 20H; aromatic protons), 5.59 (br s, 2H; C5H4), 5.05
(m, 1H; NH2), 4.53 (br s, 2H; C5H4), 4.20 (br s, 2H; C5H4), 3.97 (br s, 2H; C5H4), 3.53 (br s, 1H;
NH2), 3.12-2.62 (m, 4H; CH2N), 2.51 (br s, 1H; NH2), 1.98 ppm (br s, 1H; NH2). 13C{1H} NMR (50.3
MHz, CD2Cl2, 20 °C): δ = 199.9 (t, 2JCP = 14.4 Hz; CO), 135.9-128.4 (m; aromatic carbon atoms),
89.7 (d, 1JCP = 55.1 Hz; ipso-C5H4), 89.0 (d, 1JCP = 52.4 Hz; ipso-C5H4), 77.9 (t, JCP = 4.9 Hz; C5H4),
75.8 (t, JCP = 3.1 Hz; C5H4), 73.6 (t, JCP = 3.3 Hz; C5H4), 71.4 (t, JCP = 3.0 Hz; C5H4), 45.8 ppm (s;
CH N). 31P{1H} NMR (81.0 MHz, CD Cl , 20 °C): δ = 39.8 ppm (s). IR (Nujol): = 1960 (s) (C≡O)
휈
2
2
2
cm-1.
Synthesis of [Ru(OAc)(CO)(dppb)(en)]OAc (17)
[Ru(OAc)2(CO)(PPh3)2] (200 mg, 0.26 mmol) was suspended in CH2Cl2 (2 mL) and reacted with
dppb (122 mg, 0.29 mmol, 1.1 equiv.) stirring the mixture at RT for 6 h. En (25 µL, 0.37 mmol, 1.4
equiv.) was added to the resulting solution that was stirred at RT for further 2 h. The solvent was
reduced by evaporation under reduced pressure to about 0.5 mL and the product was precipitated by
addition of n-heptane (10 mL). The obtained solid was filtered, washed with diethyl ether (4x3 mL)
and dried under reduced pressure. Yield: 185 mg (97%). Elemental analysis calcd (%) for
C35H42N2O5P2Ru (733.75): C 57.29, H 5.77, N 3.82; found: C 57.33, H 5.80, N 3.80. 1H NMR (200.1
MHz, CD3OD, 20 °C): δ = 7.68-7.29 (m, 20H; aromatic protons), 7.27 (br s, 1H; NH2), 4.72 (m, 1H;
NH2), 4.22 (m, 1H; NH2), 4.03 (m, 1H; NCH2), 2.94-2.41 (m, 6H; PCH2 + CH2N), 2.55 (br s, 4H;
13
CH2CH2), 1.86 (s, 3H; CH3CO), 1.58 (s, 3H; CH3CO), 1.24 ppm (br s, 1H; NH2). C{1H} NMR
(50.3 MHz, CD3OD, 20 °C): δ = 203.9 (t, 2JCP = 14.8 Hz; CO), 182.8 (s; CH3CO), 182.5 (s; CH3CO),
137.8-129.1 (m; aromatic carbon atoms), 46.6 (d, 3JCP = 11.0 Hz; CH2N), 44.9 (br s; CH2N), 33.1 (br
s; CH2), 30.0 (d, 1JCP = 21.5 Hz; PCH2), 29.8 (d, 1JCP = 28.9 Hz; PCH2), 25.6 (s; CH3CO), 24.1 (s;

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DOI: 10.1039/C9DT02616A
CH3CO), 23.5 ppm (br s; CH2). P{1H} NMR (81.0 MHz, CD3OD, 20 °C): δ = 37.1 ppm (s). IR
(Nujol): = 1939 (s) (C≡O), 1558 (s) (C=O) cm-1.
휈
Synthesis of [Ru(OAc)(CO)(dppb)(ampy)]OAc (18)
Complex 11 (124 mg, 0.184 mmol) was suspended in of toluene (3 mL) and reacted with ampy (19
µL, 0.184 mmol, 1 equiv.), stirring the mixture at RT for 30 min. The resulting solution was
concentrated to about 1 mL and the product was precipitated by addition of n-heptane (5 mL). The
obtained solid was filtered and washed with diethyl ether (4x5 mL) and dried under reduced pressure.
Yield: 125 mg (87%). Elemental analysis calcd (%) for C39H42N2O5P2Ru (781.79): C 59.92, H 5.41,
N 3.58; found: C 60.03, H 5.50, N 3.50. 1H NMR (200.1 MHz, C7D8, 20 °C): δ = 8.15 (m, 1H; ortho-
3
CH of C5H4N), 7.62-6.81 (m, 22H; aromatic protons), 6.61 (d, JHH = 7.7 Hz, 1H; meta-CH of
2
3
C5H4N), 6.21 (pseudo-t, JHH = 8.8 Hz, 1H; NH2), 4.22 (dd, JHH = 12.4 Hz, JHH = 10.2 Hz, 1H;
2
3
CH2N), 3.21 (dd, JHH = 12.4 Hz, JHH = 10.7 Hz, 1H; CH2N), 3.02 (m, 1H; PCH2), 2.56 (m, 1H;
PCH2), 2.04 (s, 3H; CH3CO), 1.94 (s, 3H; CH3CO), 1.67 (m, 2H; PCH2 + NH2), 1.49-1.14 ppm (m,
5H; PCH2CH2). 13C{1H} NMR (50.3 MHz, C7D8, 20 °C): δ = 203.2 (t, 2JCP = 12.7 Hz; CO), 187.6 (s;
CH3CO), 177.0 (s; CH3CO), 159.8 (d, 3JCP = 3.8 Hz; NCCH2), 149.1 (d, 3JCP = 22.9 Hz; ortho-CH of
1
C5H4N), 135.7-120.8 (m; aromatic carbon atoms), 50.4 (s; CH2N), 30.2 (d, JCP = 33.5 Hz; PCH2),
29.8 (d, 1JCP = 36.1 Hz; PCH2), 26.1 (d, 2JCP = 2.7 Hz; CH2), 25.8 (s; CH3CO), 24.6 ppm (d, 4JCP
4.8 Hz; CH3CO). 31P{1H} NMR (81.0 MHz, C7D8, 20 °C): δ = 46.4 (d, 2JPP = 28.8 Hz), 34.0 ppm (d,
=
2J = 28.8 Hz). IR (Nujol): = 1944 (s) (C≡O), 1608 (s), 1586 (s) (C=O) cm-1.
휈
PP
Synthesis of [Ru(OAc)(CO)(dppf)(en)]OAc (19)
Complex 12 (128 mg, 0.159 mmol), was suspended in toluene (3 mL) and reacted with en (12 µL,
0.179 mmol, 1.1 equiv), heating the mixture at 90 °C for 3 h under vigorous stirring. Addition of n-
heptane (10 mL) afforded the precipitation of the product that was filtered, washed with diethyl ether
(3x5 mL) and finally dried under reduced pressure. Yield: 121 mg (88%). Elemental analysis calcd
(%) for C41H42FeN2O5P2Ru (861.66): C 57.15, H 4.91, N 3.25; found: C 57.10, H 4.90, N 3.21. 1H
NMR (200.1 MHz, CD2Cl2, 20 °C): δ = 7.90-7.61 (m, 8H; aromatic protons), 7.60-7.22 (m, 12H;
aromatic protons), 5.27 (br s partially overlapped with solvent peak, 1H; NH2), 4.55 (br s, 1H; C5H4),
4.42 (br s, 5H; C5H4), 4.16 (br s, 2H; C5H4), 2.87 (br s, 4H; CH2N), 2.62 (br s, 2H; NH2), 1.79 (br s,
13
6H; CH3CO), 1.27 ppm (br s. 1H; NH2). C{1H} NMR (50.3 MHz, CD2Cl2, 20 °C): δ = 203.2 (t,
2JCP = 15.1 Hz; CO), 181.4 (s; CH3CO), 176.6 (dd, 3JCP = 12.1 Hz, 3JCP = 5.6 Hz; CH3CO), 135.5-

Dalton Transactions
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128.5 (m; aromatic carbon atoms), 79.6 (dd, 1JCP = 65.8 Hz, 3JCP = 9.6 Hz; ipso-C5HD4)O,I:7105.1.0739(/dCt9,DJT0C2P616A
= 18.9 Hz, JCP = 4.3 Hz; C5H4), 73.0 (dt, JCP = 14.6 Hz, JCP = 2.9 Hz; C5H4), 45.7 (s; CH2N), 26.1
ppm (s; CH CO). 31P{1H} NMR (81.0 MHz, CD Cl , 20 °C): δ = 40.1 ppm (s). IR (Nujol): = 1963
휈
3
2
2
(s) (C≡O), 1617 (s), 1569 (s) (C=O) cm-1.
Synthesis of [Ru(OAc)(CO)(dppf)(ampy)]OAc (20)
18
Complex 20 was prepared following the procedure used for employing the precursor 12 (120 mg,
0.150 mmol) in place of 11. Yield: 119 mg (87%). Elemental analysis calcd (%) for
1
C45H42FeN2O5P2Ru (909.70): C 59.41, H 4.65, N 3.08; found: C 59.33, H 4.60, N 3.02. H NMR
(200.1 MHz, C7D8, 20 °C): δ = 8.68 (d, 3JHH = 4.9 Hz, 1H; ortho-CH of C5H4N), 8.00 (dd, 3JHH = 7.9
4
3
Hz, JHH = 1.5 Hz, 1H; para-CH of C5H4N), 7.46-6.79 (m, 21H; aromatic protons), 6.61 (d, JHH
=
7.8 Hz, 1H; meta-CH of C5H4N), 6.07 (pseudo-t, JHH = 9.2 Hz, 1H; NH2), 4.84 (m, 1H; CH2N), 4.77
(s, 1H; C5H4), 4.22 (s, 1H; C5H4), 3.91 (s, 1H; C5H4), 3.72 (br s, 4H; C5H4), 3.42 (s, 1H; C5H4), 2.55
(t, 3JHH = 13.5 Hz, 1H; CH2N), 2.33 (m, 1H; NH2), 1.85 (s, 3H; CH3CO), 1.67 ppm (s, 3H; CH3CO).
13C{1H} NMR (50.3 MHz, C7D8, 20 °C): δ = 210.3 (t, 2JCP = 16.4 Hz; CO), 178.4 (s; CH3CO), 177.0
(d, 3JCP = 2.7 Hz; CH3CO), 160.1 (d, 2JCP = 3.7 Hz; NCCH2), 149.1 (s; ortho-CH of C5H4N), 137.1-
121.2 (m; aromatic carbon atoms), 81.5 (d, 1JCP = 51.0 Hz; ipso-C5H4), 81.4 (d, 1JCP = 49.3 Hz; ipso-
C5H4), 77.0 (d, JCP = 4.0 Hz; C5H4), 76.5 (d, JCP = 7.3 Hz; C5H4), 75.3 (d, JCP = 7.3 Hz; C5H4), 75.0
(d, JCP = 5.2 Hz; C5H4), 74.8 (s; C5H4), 71.3 (d, JCP = 5.2 Hz; C5H4), 70.3 (d, JCP = 5.7 Hz; C5H4),
50.4 (s; CH2N), 26.1 (s; CH3CO), 24.6 ppm (d, 4JCP = 4.9 Hz; CH3CO). 31P{1H} NMR (81.0 MHz,
2
2
C7D8, 20 °C): δ = 51.2 (d, JPP = 29.1 Hz), 40.5 ppm (d, JPP = 29.1 Hz). IR (Nujol): = 1959 (s)
휈
(C≡O), 1609 (s), 1586 (s) (C=O) cm-1.
Procedure for the TH of ketones and aldehydes
The ruthenium catalyst solution used for TH was prepared by dissolving the ruthenium complexes 1-
16, 18 (0.02 mmol) in 5 mL of 2-propanol. A 0.1 M solution of NaOiPr (200 μL, 20 μmol) in 2-
propanol and the catalyst solution (250 μL, 1.0 μmol) were added to the ketone or aldehyde solution
(1.0 mmol) in 2-propanol (final volume 10 mL) and the resulting mixture was heated under reflux.
The reaction was sampled by removing an aliquot of the reaction mixture (0.5 mL), which was
quenched by addition of diethyl ether (1:1 v/v), filtered over a short silica pad, and submitted to GC
analysis. The addition of the Ru complex was considered as the start time of the reaction. The S/C
molar ratio was 1000/1, whereas the base concentration was 2 mol% respect to the substrate (0.1 M).

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DOI: 10.1039/C9DT02616A
Typical procedure for TH of acetophenone with in situ prepared catalysts from 6-14
The catalyst solutions were prepared by adding 2-propanol (5 mL) to the complexes 6-14 (0.02 mmol)
and the corresponding NN bidentate ligand (0.04 mmol). The mixtures were stirred for 30 min at
reflux. The solutions of the in situ formed catalyst were used in the TH reactions as described above.
Procedure for the HY of ketones with catalysts 1-3, 15
The HY reactions were performed in an 8 vessels Endeavor Biotage apparatus. The vessels were
charged with the ruthenium catalysts (2.5 μmol), loaded with 5 bar of N2 and slowly vented (five
times). The ketones (5 mmol) and the KOtBu solution (1 mL, 0.1 mmol, 0.1 M) in ethanol were
added. Further addition of ethanol led to a 2 M ketone solution. The vessels were purged with N2 and
H2 (three times each), then the system was charged with H2 (30 bar) and heated to 70 °C for the
required time (3 or 16 h). The S/C molar ratio was 2000/1, whereas the base concentration was 2
mol%. A similar method was applied for the reactions with other S/C (in the range 500-10000) using
the appropriate amount of catalysts, base, ligands (ligand/catalyst ratio = 2) and solvent. The reaction
vessels were then cooled to room temperature vented and purged three times with N2. A drop of the
reaction mixture was then diluted with 1 mL of methanol and analyzed by GC.
†Electronic supplementary information (ESI) available: NMR spectra of the isolated complexes
and further data of aldehyde and ketone TH and HY catalyzed by the ruthenium derivatives. For ESI
and other electronic format, see DOI: 10.1039/x0xx00000x.
Corresponding Authors. E-mails: maurizio.ballico@uniud.it, walter.baratta@uniud.it
Conflicts of interest
The authors declare no competing financial interests.
Acknowledgments
This work was supported by the Fellowship Program “Talents for an International House (TALENTS
UP)” (7th R&D FP: PEOPLE - Marie Curie Actions - COFUND) and AREA Consortium of Trieste
for a fellowship for Steven Giboulot and by the Ministero dell’Università e della Ricerca (MIUR),
PRIN 2015 program n° 20154X9ATP_005. We thank Mr. Francesco Cesaro for carrying out transfer