Bis(allyl)-ruthenium(IV) complexes with phosphinous acid ligands as catalysts for nitrile hydration reactions

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DOI: 10.1039/C6DT02375D

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Bis(allyl)-ruthenium(IV) complexes with phosphinous acid ligands

as catalysts for nitrile hydration reactions

Received 00th January 20xx,

Accepted 00th January 20xx

Eder Tomás-Mendivil,^aJavier Francos,^aRebeca González-Fernández,^aPedro J. González-Liste,^a

Javier Borge^band Victorio Cadierno*^a

DOI: 10.1039/x0xx00000x

Several mononuclear ruthenium(IV) complexes with phosphinous acid ligands [RuCl₂(η³:η³-C₁₀H₁₆)(PR₂OH)] have been

synthesized (78-86% yield) by treatment of the dimeric precursor [{RuCl(µ-Cl)(η³:η³-C₁₀H₁₆)}₂] (C₁₀H₁₆= 2,7-dimethylocta-

2,6-diene-1,8-diyl) with 2 equivalents of different aromatic, heteroaromatic and aliphatic secondary phosphine oxides

R₂P(=O)H. Compounds [RuCl₂(η³:η³-C₁₀H₁₆)(PR₂OH)] could also be prepared, in similar yields, by hydrolysis of the P-Cl bond

in the corresponding chlorophosphine-Ru(IV) derivatives [RuCl₂(η³:η³-C₁₀H₁₆)(PR₂Cl)]. In addition to NMR and IR data, the X-

ray crystal structures of representative examples are discussed. Moreover, the catalytic behaviour of complexes

[RuCl₂(η³:η³-C₁₀H₁₆)(PR₂OH)] has been investigated for the selective hydration of organonitriles in water. Best results were

achieved with complex [RuCl₂(η³:η³-C₁₀H₁₆)(PMe₂OH)], which proved to be active under mild conditions (60 °C), with low

metal loadings (1 mol%), and showing a good functional groups tolerance.

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Ruthenium is currently one of the most versatile metals

involved in catalytic organic synthesis,⁵and its combination

with PAs has already led to interesting applications. In

particular, Ackermann and Clavier demonstrated the utility of

Introduction

Phosphinous acid (PA) derivatives R₂POH have emerged in

recent years as a relevant class of auxiliary ligands for

homogeneous catalysis, with important applications in C-C

coupling (Pd, Ni), cycloaddition (Pd, Pt), hydroformylation (Rh)

and hydrogenation (Rh, Ir) reactions, to name a few.¹In 1968,

Chatt and Heaton described the preparation of the Pt(II)

complex cis-[PtCl₂(PPh₂OH)(PEt₃)] from the reaction of dimer

[{PtCl(µ-Cl)(PEt₃)}₂] with two equivalents of the secondary

phosphine oxide (SPO) Ph₂P(=O)H,²and, since then, a wide

number of transition metal complexes with PA ligands have

been synthesized following the same strategy.^1,3In solution,

the SPOs exit as a tautomeric mixture with their corresponding

PA isomers, with the former predominating under ambient

conditions.⁴In the presence of a metal, this equilibrium is

driven towards the PA tautomer by coordination (Scheme 1).^1-3

half-sandwich Ru(II) complexes of type

A as catalysts in C-H

bond arylation processes (Fig. 1).⁶Clavier also showed the

potential of the octahedral carbonyl-ruthenium(II) derivatives

B

for the cycloisomerization of arenynes,⁷while van Leeuwen

reported

a

highly efficient catalytic system for the

hydrogenation of aromatic compounds based on Ru(0)

nanoparticles stabilized by PA ligands.⁸

Fig. 1 Structures of the ruthenium(II) complexes A-C

.

Works by Oshiki, Tyler and ourselves also pointed out the

ability of complexes A,⁹and the related tethered species

(Fig.

Scheme 1 Synthesis of metal complexes with PA ligands from SPOs.

C

1),¹⁰to promote the catalytic hydration of nitriles,¹¹showing

all of them remarkable activities under challenging conditions,

i.e. in pure water and in the absence of base.¹²DFT

calculations performed by our group unveiled the key role

played by the PA ligands in this catalytic transformation.^9cAs

shown in Scheme 2, they are not mere spectators,

participating actively in the hydration process through the

formation a five-membered metallacyclic intermediate by

addition of the OH group to the coordinated nitrile. This

metallacycle is subsequently opened, through the attack of a

^a.Laboratorio de Compuestos Organometálicos y Catálisis (Unidad Asociada al

CSIC), Centro de Innovación en Química Avanzada (ORFEO-CINQA), Departamento

de Química Orgánica e Inorgánica, IUQOEM, Facultad de Química, Universidad de

Oviedo, Julián Clavería 8, E-33006 Oviedo, Spain. E-mail: vcm@uniovi.es (V.C.);

Fax: +(34) 985103446; Tel.: +(34) 985103453.

^b.Departamento de Química Física y Analítica, Centro de Innovación en Química

Avanzada (ORFEO-CINQA), Facultad de Química, Universidad de Oviedo, Julián

Clavería 8, E-33006 Oviedo, Spain.

† Electronic supplementary information (ESI) available: Copies of the NMR spectra

of complex 2d used for crystallization. CCDC reference numbers 989910 (2a),

1483673 (2d/3d), 1483674 (3c) and 1483675 (3f). For crystallographic data in CIF

or other electronic format see DOI: 10.1039/x0xx00000x

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water molecule on the phosphorus atom, releasing the amide the data obtained being in fully accord with t_Vh_iee_wp_Arr_tio_clp_eo_Os_nle_ind_e

18

DOI: 10.1039/C6DT02375D

product and regenerating the catalytically active species.

formulations (details are given in the Experimental section).

In particular, the coordination of the PA ligands to the

ruthenium(IV) center was reflected in the ³¹P{¹H} NMR spectra

by the appearance of singlet resonances strongly deshielded

(∆δ_P= 58.4-93.2 ppm) with respect to those of the starting

SPOs (see Table 1). The H and ¹³C{¹H} NMR spectra of 2a-h

1

were also very informative. Thus, in addition to the expected

resonances for the phosphinous acids substituents, the spectra

showed a single set of signals for the two allylic moieties of the

C₁₀H₁₆ligand, indicating that the two halves of the 2,7-

dimethylocta-2,6-diene-1,8-diyl skeleton are in equivalent

environments. This characteristic pattern confirms the

coordination of the PR₂OH ligands in equatorial position of the

trigonal bipyramidal ruthenium center.¹⁷On the other hand,

the IR spectra showed in all the cases the expected absorption

band for the OH unit at 3020-3197 cm^-1. For complexes 2a-b,d-

e,h, a singlet resonance at δ_H5.96-8.50 ppm associated to this

group could also be identified in their ¹H NMR spectra (for

complexes 2c,f-g this signal was not observed).

Scheme 2 The role of PA ligands in Ru-catalyzed nitrile hydration reactions.

In the context of our studies on this catalytic

transformation,^9c,10,13we also demonstrated some years ago

that the bis(allyl)-ruthenium(IV) fragment [RuCl₂(η³:η³-C₁₀H₁₆)]

(C₁₀H₁₆

=

2,7-dimethylocta-2,6-diene-1,8-diyl) offers an

excellent platform to design highly active nitrile hydration

catalysts [RuCl₂(η³:η³-C₁₀H₁₆)(PR₃)] through the appropriate

selection of the auxiliary PR₃phosphine ligand.¹⁴All these

facts, coupled with the limited number of Ru(IV)-phosphinous

acid complexes described to date in the literature,¹⁵prompted

us to study the preparation of [RuCl₂(η³:η³-C₁₀H₁₆)(PR₂OH)]

species and the evaluation of their catalytic behaviour.

Following a preliminary report,¹⁶the results derived from this

study are presented herein.

Table 1 ³¹P{¹H} NMR data for SPOs and their respective Ru(IV)-PA complexes

2a-h.^a

SPO

δ_P

Complex 2

δ_P

Ph₂P(=O)H

21.8

18.7

17.9

20.2

21.0

-17.1

23.2

38.9

2a

2b

2c

2d

2e

2f

80.2

82.1

81.6

80.9

80.8

76.1

108.5

114.8

(4-C₆H₄F)₂P(=O)H

(4-C₆H₄CF₃)₂P(=O)H

(4-C₆H₄Me)₂P(=O)H

(4-C₆H₄OMe)₂P(=O)H

(2-Furyl)₂P(=O)H

Me₂P(=O)H

Results and discussion

Synthesis and spectroscopic characterization of Ru(IV) complexes

with phosphinous acid ligands

2g

2h

Et₂P(=O)H

^aSpectra recorded in CDCl₃at 25 °C.

Following the route depicted in Scheme 1, we could synthesize

a diverse family of mononuclear complexes [RuCl₂(η³:η³-

An alternative procedure, comparatively less employed in

the literature, to synthesize metal complexes with PR₂OH

ligands is by hydrolysis of coordinated halophosphines.¹⁹In

this context, we recently shown that the chlorophosphine-

Ru(II) derivatives [RuCl₂(η⁶-p-cymene)(PR₂Cl)] can be used as

suitable precursors for the preparation of PA complexes of

C₁₀H₁₆)(PR₂OH)] (2a-h) from the reactions of the dimeric

17

precursor [{RuCl(µ-Cl)(η³:η³-C₁₀H₁₆)}₂] (

1

)

with 2 equivalents

of different aromatic, heteroaromatic and aliphatic SPOs

(Scheme 3). As expected, the chloride bridges cleavage

reactions proceeded cleanly in dichloromethane at room

temperature, affording complexes 2a-h as yellow solids (78-

86% yield) after appropriate work-up (see details in the

Experimental section). We must note in this point that all

attempts to generate species related to 2a-h employing the

type

preparation of compounds

the treatment of THF solutions of [RuCl₂(η³:η³-C₁₀H₁₆)(PR₂Cl)]

3a-f) with water, at 50 °C overnight, results in the selective

A

(see Fig. 1).²⁰This route proved to be also useful for the

(Scheme 4). Thus, we found that

2

t

(

bulkier secondary phosphine oxides Bu₂P(=O)H and Cy₂P(=O)H

formation of compounds 2a-h, which could be isolated in 72-

87% yield. The hydrolysis of the P-Cl bonds in 3a-f also takes

place at room temperature. However, longer reaction times

were in this case required, from 24 to 96 h depending on the

electronic nature of the aryl-substituents, the fastest reactions

being observed with the more electron-poor phosphine

ligands. The hydrolysis process can be considerably

accelerated at ambient temperature by carrying out the

reaction in the presence of 1 equivalent of base (K₂CO₃or

KOH; 5-10 h), but without significant yield improvements. As

shown in Scheme 4, the starting materials 3a-f were readily

failed, dimer

prolonged reflux of the reaction mixture in CH₂Cl₂.

1 being recovered unchanged even after

Scheme 3 Synthesis of the ruthenium(IV)-phosphinous acid complexes 2a-h

.

accessible from the reactions of dimer

1 with 2.2 equivalents

of

different

commercially

available

aromatic

The novel compounds 2a-h were characterized by

elemental analyses, IR and multinuclear NMR spectroscopy,

chlorophosphines.²¹The spectroscopic characterization of 3a-f

2 | J. Name., 2012, 00, 1-3

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clarity. Thermal ellipsoids are drawn at 30% probability level. Data for the

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is detailed in the Experimental section. Key features are: (i) the

presence of singlet signals in the ³¹P{¹H} NMR spectra (δ_P=

82.4-114.9 ppm), showing the expected deshielding in

comparison with those of the corresponding free

intramolecular H-bond are as follows: O1-H1o = 0.95(2) Å, Cl2-H1o = 2.00(3) Å,

DOI: 10.1039/C6DT02375D

Cl2-O1 = 2.917(2) Å and Cl2-H1o-O1 = 164(2)°.

chlorophosphines (∆δ_P

= 29.4-64.6 ppm), and (ii) the

equivalence in the ¹H and ¹³C{¹H} NMR spectra of the two

halves of the octadienediyl ligand C₁₀H₁₆, which confirms again

the formation of equatorial adducts.¹⁷

Fig. 3 ORTEP view of the structure of 2d/3d showing the crystallographic

labelling scheme. Hydrogen atoms, except that on O1, have been omitted for

clarity. Thermal ellipsoids are drawn at 30% probability level. Data for the

intramolecular H-bond are as follows: O1-H1o = 1.14(8) Å, Cl2-H1o = 1.91(8) Å,

Cl2-O1 = 2.928(9) Å and Cl2-H1o-O1 = 146(5)°.

Table 2 Selected bond distances (Å) and angles (°) for compounds 2a, 2d/3d,

3c and 3f.^a

Scheme 4 Synthesis of the chlorophosphine-Ru(IV) complexes 3a-f and their

hydrolysis.

2a

2d/3d

3c

3f

Bond distances

Ru-Cl1

Ru-Cl2

Ru-C1

Ru-C2

Ru-C4

Ru-C7

Ru-C8

Ru-C9

C1-C2

C2-C4

C7-C8

C8-C9

Ru-P1

P1-O1

P1-Cl3

2.4178(6)

2.4540(6)

2.225(2)

2.272(2)

2.279(2)

2.286(2)

2.277(3)

2.196(3)

1.414(3)

1.400(3)

1.400(4)

1.412(4)

2.3784(7)

1.604(2)

---

2.409(1)

2.446(1)

2.215(4)

2.291(4)

2.283(4)

2.275(4)

2.272(4)

2.229(4)

1.416(6)

1.391(6)

1.403(6)

1.408(6)

2.383(1)

1.616(9)

1.99(2)

2.4224(9)

2.412(1)

2.251(4)

2.300(4)

2.267(4)

2.291(4)

2.290(4)

2.213(4)

1.402(6)

1.410(6)

1.398(6)

1.418(6)

2.3863(9)

---

2.420(2)

2.423(2)

2.220(7)

2.296(6)

2.272(7)

2.279(7)

2.285(7)

2.211(7)

1.41(1)

1.39(1)

1.42(1)

2.343(2)

---

X-Ray crystal structures

To gain further insights into the structure of these compounds,

single-crystal X-ray diffraction studies on [RuCl₂(η³:η³-

C₁₀H₁₆)(PPh₂OH)]

(

2a

)

and

[RuCl₂(η³:η³-C₁₀H₁₆){P(4-

C₆H₄Me)₂OH}] (2d) were undertaken. X-ray quality crystals

were obtained in both cases by slow diffusion of hexanes into

a saturated solution of the complex in dichloromethane.

ORTEP plots of the molecular structures are shown in Fig. 2

and 3, respectively, while selected bonding parameters are

listed in Table 2. In the case of complex 2d a substitutional

disorder was detected, in which approximately 23% of the

lattice points in the crystal were occupied not with the PA

complex 2d, but with the chlorophosphine derivative 3d. The

sample of 2d employed for crystallization was prepared by

hydrolysis of 3d and, unfortunately, traces of the starting

material were still present, leading to a mixed crystal

containing both species (copies of the NMR spectra of this

sample are given in the ESI file). Both 2d and 3d are shown as a

composite structure in Fig. 3. Apart from the P-OH/P-Cl units,

changes in the rest of bond lengths and angles are so slight as

to be undetectable.

2.044(1)

2.037(2)

Bond angles

Cl1-Ru-Cl2

Cl1-Ru-P1

Cl1-Ru-C*

Cl1-RuC**

Cl2-Ru-P1

Cl2-Ru-C*

Cl2-Ru-C**

P1-Ru-C*

P1-Ru-C**

C*-Ru-C**

C1-C2-C4

C7-C8-C9

Ru-P1-O1

Ru-P1-Cl3

172.41(2)

86.48(2)

95.53(2)

88.20(2)

86.11(2)

88.92(2)

93.51(2)

113.33(2)

115.56(2)

131.11(1)

116.4(2)

117.2(2)

109.93(8)

---

172.07(4)

85.21(3)

88.80(3)

96.10(3)

87.15(4)

92.69(3)

88.84(3)

116.34(4)

113.02(3)

130.63(2)

116.7(4)

116.4(4)

108.7(3)

113.0(5)

174.25(3)

83.07(3)

94.79(3)

89.24(3)

91.19(3)

87.99(3)

92.79(3)

115.78(3)

113.63(3)

130.56(1)

116.3(4)

115.8(4)

---

171.87(6)

80.25(6)

89.77(1)

95.02(1)

91.63(6)

93.73(1)

88.20(1)

112.56(1)

116.09(1)

131.23(1)

115.8(6)

116.7(7)

---

113.32(5)

115.67(9)

^aC* and C** denote the centroids of the allyl units (C1-C2-C4, and C7-C8-C9,

respectively).

The geometry about the respective ruthenium(IV) atoms is

best described as a distorted trigonal bipyramid by considering

the allyl groups as monodentate ligands bound to the metal

through their centres of mass (C* and C**; see footnote of

Table 2). The chloride ligands occupy the axial positions with

Cl1-Ru-Cl2 bond angles of 172.41(2)° (2a) and 172.07(4)°

Fig. 2 ORTEP view of the structure of complex 2a showing the crystallographic

labelling scheme. Hydrogen atoms, except that on O1, have been omitted for

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(

2d/3d), while the octadienediyl moiety and the P-donor parameters found for the RuCl₂(η³:η³-C₁₀H₁₆) units were very

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ligand are located at the equatorial sites. Both allyl groups of similar to those discussed above for 2a a^Dn^Od^I:2¹⁰d^.1/⁰3³d⁹.^/CT⁶h^De^T0P²1³-⁷C⁵l^D3

the organic C₁₀H₁₆fragment are η³-bound to the ruthenium lengths observed (2.044(1) and 2.037(2) Å, respectively) also

atom with Ru-C and C-C distances in the ranges 2.196(3)- fall within the expected range for P-Cl bonds.²⁵

2.291(4) and 1.391(6)-1.416(6) Å, respectively (Table 2). These

values, together with the internal allylic C-C-C angles (116.4(2)- Catalytic activity in nitrile hydration reactions

117.2(2)°), compare well with those observed in other

structures containing the “Ru(η³:η³-C₁₀H₁₆)” unit.^14,22The Ru-P

bond lengths observed, of 2.3784(7) (2a) and 2.383(1) Å

Hydration of benzonitrile: Catalysts screening and optimization of

the reaction conditions

(

2d/3d), are slightly longer to those found in the crystal The ability of the PA-Ru(IV) complexes 2a-h to promote the

structures of related Ru(II) complexes [RuCl₂(η⁶-p- catalytic hydration of nitriles to primary amides was next

cymene)(PAr₂OH)] (Ar = Ph, 4-C₆H₄F; 2.3120(8) and 2.3009(8) evaluated. Initial experiments were performed by adding the

Å, respectively), while the phosphorus-oxygen distances are corresponding ruthenium catalyst (2 mol%) to a 0.33 M

almost identical and in agreement with the nature of a single aqueous solution of benzonitrile, and subsequent heating of

bond (ca. 1.60 Å).^6cAs observed for these ruthenium(II) the mixture in an oil bath at 80 °C for 2 hours. As shown in

complexes, an intramolecular H-bonding interaction of Table 3 (entries 1-8), all the complexes synthesized proved to

moderate intensity (mostly electrostatic)²³between the OH be active, providing benzamide as the unique reaction product

unit and one of the chloride ligands was found in both (in no case benzoic acid was detected by GC in the crude

structures (see captions of Fig. 2 and 3 for details).²⁴

reaction mixtures). Among them, best results were obtained

with [RuCl₂(η³:η³-C₁₀H₁₆)(PMe₂OH)] (2g), which was able to

generate benzamide quantitatively (entry 7 in Table 3).

Concerning the effect of the PA substituents on the catalytic

activity of these complexes, a clear pattern could not be

drawn. Although higher yields were in general reached with

the more basic P-donor ligands, the differences observed

between complexes 2g and 2h indicate that steric factors also

play an important role in the reaction (entry 7 vs 8 in Table 3).

In the case of 2f, the presence of the potentially coordinating

2-furyl units in the PA ligand, able to compete with the nitrile

for binding the metal, could explain the remarkably low

activity shown by this complex (entry 6 in Table 3).

As expected,²⁰the chlorophosphine-Ru(IV) derivatives 3a-f

also catalyze the hydration process (entries 9-14 in Table 3).

However, compared to their phosphinous acid counterparts

2a-f, all of them showed a lower effectiveness since they

require of an induction period to generate the active species

2a-f by hydrolysis of the P-Cl bond. Significant improvements

in activity were observed by carrying out the reactions in the

presence of 2 mol% of K₂CO₃due to the faster conversion of

3a-f into 2a-f in basic media (entries 15-20 vs 9-14 in Table 3).

On the other hand, the key role played by the R₂POH ligands

was clearly evidenced from the results collected in entries 21-

24 (Table 3). Thus, when complex [RuCl₂(η³:η³-C₁₀H₁₆)(PPh₃)]

Fig. 4 ORTEP view of the structure of complex 3c showing the crystallographic

labelling scheme. Hydrogen atoms have been omitted for clarity. Thermal

ellipsoids are drawn at 30% probability level.

(4), containing a non-cooperative phosphine ligand, was

employed, under identical experimental conditions, only traces

of benzamide were detected by GC after 2 h of heating (entry

21 in Table 3). Very poor results were also obtained with

[RuCl₂(η³:η³-C₁₀H₁₆)(THPA)] (

THDP)] (

5

) and [{RuCl₂(η³:η³-C₁₀H₁₆)}₂(µ-

) (entries 22-23 in Table 3 and Fig. 6). In a previous

6

study, we had shown that these two complexes were able to

hydrate benzonitrile in 92-99% yield after 2 h performing the

reactions at 100 °C with a metal loading of 5 mol%, and their

good performances were ascribed to the cooperative

participation of the nitrogenated phosphines, which facilitate

the nucleophilic addition of the water molecule on the metal-

coordinated nitrile through H-bonding.¹⁴The higher activities

shown by 2a-h under milder conditions suggest that the

Fig. 5 ORTEP view of the structure of complex 3f showing the crystallographic

labelling scheme. Hydrogen atoms have been omitted for clarity. Thermal

ellipsoids are drawn at 30% probability level.

The structures of the chlorophosphine-Ru(IV) complexes

[RuCl₂(η³:η³-C₁₀H₁₆)(PR₂Cl)] (R = 4-C₆H₄CF₃

(3c), 2-furyl (3f))

were also unequivocally confirmed by single-crystal X-ray

diffraction (see Fig. 4 and 5, and Table 2). The geometrical

4 | J. Name., 2012, 00, 1-3

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reaction pathway depicted in Scheme 2 is probably operating 3 days were in this case required (entry 4 in Tab_Vle_iew4_A)_r._ticA_lels_Oo_nlio_nef

DOI: 10.1039/C6DT02375D

with these Ru(IV) complexes. The poor results obtained with note, a respectable TON of 500 could be achieved using 0.2

the phosphite complex [RuCl₂(η³:η³-C₁₀H₁₆){P(OMe)₃}] (

7

) also mol% of 2g, and performing the hydration reaction at 60 °C,

support the active participation of the OH bond (entry 24 in conditions in which quantitative formation of benzamide was

Table 3), and discard its simple role as a H-bond acceptor.

again observed (entry 5 in Table 4).

Table 3 Catalytic hydration of benzonitrile using Ru(IV) complexes^a

Table 4 Catalytic hydration of benzonitrile using the Ru(IV) complex 2g^a

Yield^b

TOF (h^-1)

Entry

mol% of Ru

T (°C)

t (h)

Yield (%)^b

TOF (h^-1)

Entry

Catalyst

1

2

3

4

5

2

1

80

60

20

60

1.1

2.3

3

72

24

> 99

45.4

43.5

33.3

1.4

1

2

3

4

5

6

7

8

[RuCl₂(η³:η³-C₁₀H₁₆)(PPh₂OH)] (2a)

86%

88%

56%

89%

87%

30%

>99%

88%

67%

60%

48%

72%

66%

13%

84%

93%

71%

92%

85%

41%

21.5

22.0

14.0

22.2

21.8

7.5

25.0

22.0

16.7

15.0

12.0

18.0

16.5

3.3

21.0

23.2

17.8

23.0

21.3

10.2

[RuCl₂(η³:η³-C₁₀H₁₆){P(4-C₆H₄F)₂OH}] (2b)

[RuCl₂(η³:η³-C₁₀H₁₆){P(4-C₆H₄CF₃)₂OH}] (2c)

[RuCl₂(η³:η³-C₁₀H₁₆){P(4-C₆H₄Me)₂OH}] (2d)

[RuCl₂(η³:η³-C₁₀H₁₆){P(4-C₆H₄OMe)₂OH}] (2e)

[RuCl₂(η³:η³-C₁₀H₁₆){P(2-furyl)₂OH}] (2f)

[RuCl₂(η³:η³-C₁₀H₁₆)(PMe₂OH)] (2g)

[RuCl₂(η³:η³-C₁₀H₁₆)(PEt₂OH)] (2h)

0.2

20.8

a

Reactions were performed under Ar atmosphere starting from 1 mmol of

benzonitrile (0.33 M in water). ^bDetermined by GC (uncorrected GC areas).

9

[RuCl₂(η³:η³-C₁₀H₁₆)(PPh₂Cl)] (3a)

Scope of the catalytic reaction employing complex [RuCl₂(η³:η³-

C₁₀H₁₆)(PMe₂OH)] (2g)

10

11

12

13

14

15^c

16^c

17^c

18^c

19^c

20^c

21

22

23

24

[RuCl₂(η³:η³-C₁₀H₁₆){P(4-C₆H₄F)₂Cl}] (3b)

[RuCl₂(η³:η³-C₁₀H₁₆){P(4-C₆H₄CF₃)₂Cl}] (3c)

[RuCl₂(η³:η³-C₁₀H₁₆){P(4-C₆H₄Me)₂Cl}] (3d)

[RuCl₂(η³:η³-C₁₀H₁₆){P(4-C₆H₄OMe)₂Cl}] (3e)

[RuCl₂(η³:η³-C₁₀H₁₆){P(2-furyl)₂Cl}] (3f)

[RuCl₂(η³:η³-C₁₀H₁₆)(PPh₂Cl)] (3a)

To define the scope of this catalytic transformation, other

aromatic nitriles were subjected to the action of complex

[RuCl₂(η³:η³-C₁₀H₁₆)(PMe₂OH)] (2g) (entries 2-12 in Table 5).

Thus, we were pleased to find that almost all the substrates

tested could be selectively converted into the corresponding

primary amides, in ≥ 89% GC yield (≥ 71% isolated), performing

the catalytic reactions at 60 ᵒC with 1 mol% of 2g. A slight

influence of the electronic properties of the aryl rings was

observed, with those substrates containing electron-donating

groups showing a lower reactivity (e.g., entry 10 vs 6 in Table

5). Substitution in ortho position also led to a less efficient

hydration (e.g., entry 3 vs 4-5 in Table 5). Indeed, in the case of

2-methylbenzonitrile (entry 8 in Table 5), an increase of the

ruthenium loading to 3 mol% was needed to obtain 2-

methylbenzamide in high yield. Over-hydrolysis to carboxylic

acids was in no case observed.

RuCl₂(η³:η³-C₁₀H₁₆){P(4-C₆H₄F)₂Cl}] (3b)

[RuCl₂(η³:η³-C₁₀H₁₆){P(4-C₆H₄CF₃)₂Cl}] (3c)

[RuCl₂(η³:η³-C₁₀H₁₆){P(4-C₆H₄Me)₂Cl}] (3d)

[RuCl₂(η³:η³-C₁₀H₁₆){P(4-C₆H₄OMe)₂Cl}] (3e)

[RuCl₂(η³:η³-C₁₀H₁₆){P(2-furyl)₂Cl}] (3f)

[RuCl₂(η³:η³-C₁₀H₁₆)(PPh₃)] (4)

traces --

15%

8%

5%

[RuCl₂(η³:η³-C₁₀H₁₆)(THPA)] (5)

3.8

2.0

1.3

[{RuCl₂(η³:η³-C₁₀H₁₆)}₂(µ-THDP)] (6)

[RuCl₂(η³:η³-C₁₀H₁₆){P(OMe)₃}] (7)

a

Reactions were performed under Ar atmosphere starting from 1 mmol of

benzonitrile (0.33 M in water). ^bDetermined by GC (uncorrected GC areas). ^c

Reaction performed in the presence of 2 mol% of K₂CO₃.

Complex 2g was also effective in the hydration of a wide

range of heteroaromatic nitriles, including pyridyl (entries 13-

15 in Table 5), pyrazyl (entry 16 in Table 5), pyridazyl (entry 17

in Table 5), quinolyl (entry 18 in Table 5), thienyl (entries 19-20

in Table 5), furyl (entries 21-22 in Table 5), pyrrolyl (entry 23 in

Table 5) and indolyl (entries 24-25 in Table 5) derivatives.

However, for the latter, an increase of the temperature was

needed (100 °C) to attain good conversions due to their

insolubility in water at 60 °C. Similarly, the hydration of 3-

cyanocoumarin with 1 mol% of 2g only proceeded effectively

at 100 °C and long reaction time (entry 26 in Table 5). Complex

2g was also active in the hydration of vinylic and non-

conjugated nitriles at 60 °C (entries 27-34 in Table 5), thus

confirming the general applicability of this catalyst. As

observed with the benzonitrile derivatives, influence of the

electronic properties of the substrates was also evidenced.

Thus, in comparison with acetonitrile (entry 29 in Table 5),²⁸

chloroacetonitrile (entry 30 in Table 5), trichloroacetonitrile

(entry 31 in Table 5) and phenoxyacetonitrile (entry 32 in Table

5) were hydrated much faster as a result of the higher

Fig. 6 Structure of the bis(allyl)-ruthenium(IV) complexes 5 and 6.

To assess more accurately the catalytic potential of the

most active complex [RuCl₂(η³:η³-C₁₀H₁₆)(PMe₂OH)]

2g),

(

additional experiments with benzonitrile were performed

(Table 4). First, a detailed monitoring by GC of the reaction at

80 °C with 2 mol% of this complex indicated that benzonitrile is

completely consumed after ca. 1 h (entry 1 in Table 4), leading

to a TOF of 45.4 h^-1. A similar TOF value was reached when the

ruthenium loading was halved, with quantitative formation of

benzamide in 2.3 h (entry 2 in Table 4). Even at 60 °C, a rapid

conversion of benzonitrile into benzamide was observed by

employing 1 mol% of 2g (TOF = 33.3 h^-1; entry 3 in Table 4). We

would like to point here that ruthenium catalysts capable of

operating as fast below 100 °C, in pure water and under base-

free conditions, are relatively rare in the literature.^26,27

Furthermore, the reaction could also be completed at r.t., but

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electrophilicity of the nitrile carbon atom in these substrates, to generate selectively the monohydrated pro_Vd_ieu_wct_As_rtic(_lelo_Ow_nlie_ner

31

DOI: 10.1039/C6DT02375D

due to the inductive effects of the chlorine atom and phenoxy temperatures, Ru loadings or reaction times) failed.

group, respectively. For phenoxyacetonitrile, an impressive

TOF value of 1188 h^-1was attained at this mild temperature.

Table 5 Catalytic hydration of nitriles to amides using the Ru(IV) complex 2g^a

Entry

Nitrile

t (h)

Yield (%)^b

TOF (h^-1)

1

2

3

4

5

6

R = Ph

R = C₆F₅

3

0.5

7

2

> 99 (89)

98 (85)

98 (80)

> 99 (74)

97 (75)

98 (80)

99 (75)

89 (71)

95 (87)

97 (81)

95 (73)

99 (75)

97 (74)

98 (84)

98 (90)

98 (81)

96 (84)

99 (84)

99 (71)

97 (79)

> 99 (72)

> 99 (76)

99 (77)

98 (78)

98 (77)

91 (80)

> 99 (83)

97 (65)

> 99 (87)

> 99 (80)

99 (84)

99 (92)

> 99 (87)

> 99 (80)

33.3

196.0

14.0

50.0

48.5

98.0

198.0

1.8

31.7

12.1

13.6

24.8

16.2

196.0

98.0

49.0

12.0

99.0

198.0

97.0

200.0

33.0

19.6

3.8

R = 2-C₆H₄Cl

R = 3-C₆H₄Cl

R = 4-C₆H₄Br

R = 4-C₆H₄(COMe)

R = 3-C₆H₄NO₂

R = 2-C₆H₄Me

R = 4-C₆H₄Me

R = 4-C₆H₄OMe

R = 4-C₆H₄OH

R = 4-C₆H₄SMe

R = 2-Pyridyl

R = 3-Pyridyl

R = 4-Pyridyl

R = 2-Pyrazyl

R = 3-Pyridazyl

R = 2-Quinolyl

R = 2-Thienyl

R = 3-Thienyl

R = 5-Me-2-furyl

R = 3-Furyl

R = 2-Pyrrolyl

R = 3-Indolyl

R = 5-Indolyl

R = 3-Cumarinyl

R = CH=CH₂

R = n-C₆H₁₃

R = CH₃

R = CH₂Cl

R = CCl₃

R = CH₂OPh

R = CH₂-2-thienyl

R = CH₂CH₂OPh

1

Scheme 5 Catalytic synthesis of rufinamide (9) and ibuprofenamide (10).

7

0.5

16

3

8

7

4

6

0.5

1

2

8

1

0.5

1

0.5

3

5

24

3

6

0.25

1

5 min

1

8^c

9

10

11

12

13

14

15

16

17

18

19

20

21

22

23

24^d

25^d

26^d

27

28

29

30

31

32

33

34

Scheme 6 Catalytic hydration of dinitriles using complex 2g

.

Complex 2g was also able to promote the challenging

hydration of α-hydroxynitriles (cyanohydrins), substrates very

difficult to hydrate because in polar media they degrade into

the corresponding carbonyl compounds and HCN. The vast

majority of nitrile hydration catalysts reported to date are

inactive towards cyanohydrins due to their poisoning by

cyanide.³²As shown in Scheme 7, using 5 mol% of 2g, and

performing the reactions at r.t. to minimize the decomposition

of the substrates, complete conversion of lactonitrile (R = Me)

and 2-hydroxybutyronitrile (R = Et) into the corresponding α-

hydroxyamides could be achieved after 72 h of stirring. In the

case of lactonitrile, a 92% conversion is already reached after 7

h.³³However, we must note that the system was completely

inoperative with aromatic cyanohydrins, such as

mandelonitrile (R = Ph). A rapid discoloration of the solution,

indicative of the poisoning of the catalyst by cyanide, was in

this case observed (in the previous examples the solution

remained yellow all along the process).

33.3

16.2

16.7

400.0

99.0

1188.0

100.0

16.7

6

a

Reactions were performed under Ar atmosphere starting from 1 mmol of

b

the corresponding nitrile (0.33

M

in water).

Determined by GC

(uncorrected GC areas); Isolated yields after work-up are given in brackets. ^c

Reaction performed with 3 mol% of 2g. ^dReaction performed at 100 °C.

Primary amides of pharmacological interest, such as the

29

antiepileptic drug rufinamide

(9

)

and the NSAID

ibuprofenamide (10),³⁰could also been obtained in high yield

by catalytic hydration of 4-cyano-1-(2,6-difluorobenzyl)-1H-

1,2,3-triazole (7) and 2-(4-isobutylphenyl)propionitrile (8),

respectively, using 2g (Scheme 5). Both reactions proceeded

cleanly at 60 °C with a metal loading of 1 mol%, conditions that

are much milder than those described in previous works.^13d,e,h

The behaviour of 2g towards dinitriles was also explored

(Scheme 6). Thus, under the standard reaction conditions, the

hydration of

adiponitrile, fumaronitrile and 1,3-

dicyanobenzene led to the corresponding diamides, which

could be isolated in 71-85% yield. Unfortunately, all attempts

Scheme 7 Catalytic hydration of lactonitrile and 2-hydroxybutyronitrile.

6 | J. Name., 2012, 00, 1-3

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ARTICLE

Recycling of complex [RuCl₂(η³:η³-C₁₀H₁₆)(PMe₂OH)] (2g)

sealed-tube techniques. Organic solvents were dried by

View Article Online

34

standard methods and distilled under a^Drg^Oo^I:n¹⁰b^.1e⁰f³o⁹r^/e^C6u^Ds^Te⁰.²³⁷A^5Dll

Finally, as already discussed in our preliminary

communication,¹⁶the recycling of complex 2g is also possible

since, in most cases, after completion of the hydration

reaction, selective crystallization of the amide takes place by

cooling the mixture at r.t., or at 0 °C in an ice bath, remaining

the organometallic catalyst dissolved in water. Using

pentafluorobenzamide as model substrate, the aqueous phase

containing 2g could be reused 10 consecutive times, with loss

of activity being observed only after the sixth cycle (cumulative

TON after the 10 cycles = 853; see Fig. 7 and the Experimental

section). Such a recycling capacity evidences the remarkable

stability of this complex.

reagents were obtained from commercial suppliers and used

as received, with the exception of complexes [{RuCl(µ-

Cl)(η³:η³-C₁₀H₁₆)}₂]

(1

),³⁵[RuCl₂(η³:η³-C₁₀H₁₆)(PPh₃)]

(4

),³⁶

[RuCl₂(η³:η³-C₁₀H₁₆)(THPA)]

(5

),¹⁴[{RuCl₂(η³:η³-C₁₀H₁₆)}₂(µ-

14

THDP)] (

6

)

and [RuCl₂(η³:η³-C₁₀H₁₆){P(OMe)₃}] (

7

),³⁷the SPOs

R₂P(=O)H (R = Ph,³⁸4-C₆H₄F,³⁸4-C₆H₄CF₃,³⁹4-C₆H₄Me,³⁸4-

C₆H₄OMe,³⁸2-Furyl,⁴⁰Me,⁴¹Et,^{41 t}Bu,³⁸Cy³⁸), and the nitrile

8 ⁴²

which were prepared following the methods reported in

,

the literature. GC measurements were performed with a

Hewlett-Packard HP6890 equipment using a Supelco Beta-

Dex^TM120 column (30 m length; 250 µm diameter). Elemental

analyses were provided by the Analytical Service of the

Instituto de Investigaciones Químicas (IIQ-CSIC) of Seville.

Infrared spectra were recorded on a Perkin-Elmer 1720-XFT

spectrometer. NMR spectra were recorded on Bruker DPX-300

or AV400 instruments. The chemical shift values (δ) are given

in parts per million and are referred to the residual peak of the

deuterated solvent employed (¹H and ¹³C), to an external 85%

aqueous H₃PO₄solution (³¹P), or to the CFCl₃standard (¹⁹F).

DEPT experiments have been carried out for all the

compounds reported. The numberings employed for the

protons and carbons of the 2,7-dimethylocta-2,6-diene-1,8-diyl

skeleton are as follows:

Fig. 7 Reuse of the aqueous solution containing 2g in the hydration reaction of

pentafluorobenzonitrile. Separation of the pentafluorobenzamide formed by

crystallization at 0 ⁰C in an ice bath. Reaction conditions identical to those

indicated in Table 5 (0.5 h of reaction in each cycle).

Conclusions

The synthesis and characterization of a family of ruthenium(IV)

derivatives with phosphinous acid (PA) ligands, namely

[RuCl₂(η³:η³-C₁₀H₁₆)(PR₂OH)], have been presented. These

complexes are readily accessible in high yields by treatment of

Synthesis of [RuCl₂(η³:η³-C₁₀H₁₆)(PR₂OH)] (R = Ph (2a), 4-C₆H₄F

(2b), 4-C₆H₄CF₃(2c), 4-C₆H₄Me (2d), 4-C₆H₄OMe (2e), 2-Furyl

(2f), Me (2g), Et (2h))

A purple solution of the dimeric precursor [{RuCl(µ-Cl)(η³:η³-

the dimeric precursor [{RuCl(µ-Cl)(η³:η³-C₁₀H₁₆)}₂] with

2

equivalents of different aromatic, heteroaromatic and aliphatic

secondary phosphine oxides R₂P(=O)H, or, alternatively, by

hydrolysis of the P-Cl bond in the corresponding

C₁₀H₁₆)}₂] (1) (0.200 g, 0.32 mmol) in dichloromethane (50 mL)

[RuCl₂(η³:η³-

was treated, at room temperature, with the corresponding

secondary phosphine oxide R₂P(=O)H (0.64 mmol) for 48 h.

The solvent was then removed under reduced pressure. For

2a-f, the resulting yellow solid was washed with hexanes (2 x

10 mL) and diethyl ether (2 x 10 mL), and dried under vacuum.

For 2g,h, the resulting oily residue was dissolved in diethyl

ether (30 mL) and filtered. The filtrate was evaporated to

dryness and the yellow syrup formed washed with hexanes (10

mL) to afford a yellow solid, which was dried under vacuum.

(2a): Yield: 0.269 g (82%). IR (KBr): ν = 3035 (br, O-H) cm^-1.

chlorophosphine-Ru(IV)

derivatives

C₁₀H₁₆)(PR₂Cl)]. In addition, their catalytic behaviour has been

investigated for the selective hydration of organonitriles, being

all of them able to operate in pure water without the

assistance of any acidic or basic additive. Best results were

achieved with complex [RuCl₂(η³:η³-C₁₀H₁₆)(PMe₂OH)], which

proved to be active under remarkably mild conditions (60 °C),

with low metal loadings (1 mol%), and showing a good

functional groups tolerance and recycling capacity. In

summary, the results reported herein represent a new

example of the enormous potential that PA ligands offer in

homogeneous catalysis.

1

³¹P{¹H} NMR (CDCl₃): δ = 80.2 (s) ppm. H NMR (CDCl₃): δ =

8.14 (m, 2H, Ph), 8.03 (m, 2H, Ph), 7.75 (s, 1H, OH), 7.42 (m,

3

6H, Ph), 5.16 (m, 2H, H₃and H₈), 3.85 (d, 2H, J_PH= 10.4 Hz, H₁

3

and H₉), 3.55 (m, 2H, H₅and H₇), 3.15 (d, 2H, J_PH= 3.3 Hz, H₂

and H₁₀), 2.73 (m, 2H, H₄and H₆), 2.14 (s, 6H, Me) ppm. ¹³C{¹H}

Experimental

1

NMR (CDCl₃): δ = 140.8 (d, J_CP= 53.6 Hz, C_ipsoof Ph), 139.1 (d,

¹J_CP= 54.3 Hz, C_ipsoof Ph), 129.7 (m, CH_paraand CH_orthoor CH_meta

of Ph), 128.2 (d, J_PC= 10.5 Hz, CH_orthoor CH_metaof Ph), 128.0 (d,

J_PC= 10.5 Hz, CH_orthoor CH_metaof Ph), 125.2 (s, C₂and C₇), 107.7

General methods

All the manipulations were performed under argon

atmosphere using vacuum-line and standard Schlenk or

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(br, C₃and C₆), 67.1 (s, C₁and C₈), 37.2 (s, C₄and C₅), 21.1 (s, J_PC= 10.7 Hz, CH_orthoor CH_metaof C₆H₄OMe), 131.5_V(_ied_w, _AJ_r_P_t_C_icl=_{e O}1_n0_lin.9_e

1

Me) ppm. Elemental analysis calcd. (%) for C₂₂H₂₇Cl₂OPRu: C Hz, CH_orthoor CH_metaof C₆H₄OMe), 131.4^D(d^O,^{I: 1}J⁰_P^._C¹⁰=³⁹5^/8^C.⁶5^DH^T0z², ³C⁷_i⁵_ps^D_o

51.77, H 5.33; found: C 51.59, H 5.38. (2b): Yield: 0.297 g of C₆H₄OMe), 124.6 (s, C₂and C₇), 113.8 (d, J_PC= 13.6 Hz,

(85%). IR (KBr): ν = 3038 (br, O-H) cm^-1. ³¹P{¹H} NMR (CDCl₃): δ CH_orthoor CH_metaof C₆H₄OMe), 113.6 (d, J_PC= 13.6 Hz, CH_orthoor

= 82.1 (s) ppm. ¹⁹F{¹H} NMR (CDCl₃): δ = -110.0 (s), -110.4 (s) CH_metaof C₆H₄OMe), 107.3 (br, C₃and C₆), 67.6 (br, C₁and C₈),

1

ppm. H NMR (CDCl₃): δ = 8.12 (m, 2H, C₆H₄F), 8.00 (m, 2H, 54.5 (s, C₆H₄OMe), 54.4 (s, C₆H₄OMe), 36.9 (s, C₄and C₅), 20.8

C₆H₄F), 7.84 (s, 1H, OH), 7.10 (m, 4H, C₆H₄F), 5.16 (m, 2H, H₃(s, Me) ppm. Elemental analysis calcd. (%) for C₂₄H₃₁O₃Cl₂PRu:

3

and H₈), 3.80 (d, 2H, J_PH= 10.5 Hz, H₁and H₉), 3.57 (m, 2H, H₅C 50.53, H 5.48; found: C 50.40, H 5.43. (2f): Yield: 0.251 g

and H₇), 3.12 (br, 2H, H₂and H₁₀), 2.73 (m, 2H, H₄and H₆), 2.15 (80%). IR (KBr): ν = 3119 (br, O-H) cm^-1. ³¹P{¹H} NMR (CDCl₃): δ

1

(s, 6H, Me) ppm. ¹³C{¹H} NMR (CDCl₃): δ = 163.8 (d, ¹J_FC= 250.6 = 76.1 (s) ppm. H NMR (CDCl₃): δ = 7.78 (br, 1H, furyl), 7.73

1

Hz, C_paraof C₆H₄F), 163.6 (d, J_FC= 252.5 Hz, C_paraof C₆H₄F), (br, 1H, furyl), 7.05 (br, 1H, furyl), 6.96 (br, 1H, furyl), 6.54 (br,

1

136.5 (d, J_PC= 52.4 Hz, C_ipsoof C₆H₄F), 134.8 (d, J_PC= 56.3 Hz, 1H, furyl), 6.50 (br, 1H, furyl), 5.14 (m, 2H, H₃and H₈), 4.26 (d,

C_ipsoof C₆H₄F), 131.8 (m, CH_orthoor CH_metaof C₆H₄F), 125.3 (s, C₂2H, ³J_PH= 10.2 Hz, H₁and H₉), 3.56 (m, 2H, H₅and H₇), 3.15 (d,

3

and C₇), 115.4 (m, CH_orthoor CH_metaof C₆H₄F), 108.1 (br, C₃and 2H, J_PH= 4.2 Hz, H₂and H₁₀), 2.80 (m, 2H, H₄and H₆), 2.21 (s,

C₆), 67.1 (s, C₁and C₈), 37.2 (s, C₄and C₅), 21.1 (s, Me) ppm. 6H, Me) ppm; OH signal not observed. ¹³C{¹H} NMR (CDCl₃): δ =

Elemental analysis calcd. (%) for C₂₂H₂₅Cl₂F₂OPRu: C 48.36, H 147.1 (m, C and CH of furyl), 120.7 (d, J_PC= 15.1 Hz, CH of

4.61; found: C 48.44, H 4.58. (2c): Yield: 0.356 g (86%). IR (KBr): furyl), 120.2 (d, J_PC= 14.9 Hz, CH of furyl), 110.7 (d, J_PC= 7.1 Hz,

ν = 3047 (br, O-H) cm^-1. ³¹P{¹H} NMR (CDCl₃): δ = 81.6 (s) ppm. CH of furyl), 110.6 (d, J_PC= 7.1 Hz, CH of furyl), 123.9 (s, C₂and

¹⁹F{¹H} NMR (CDCl₃): δ = -63.0 (s), -63.1 (s) ppm. ¹H NMR C₇), 108.9 (d, ²J_PC= 11.2 Hz, C₃and C₆), 64.8 (s, C₁and C₈), 37.0

(CDCl₃): δ = 8.30 (m, 2H, C₆H₄CF₃), 8.18 (m, 2H, C₆H₄CF₃), 7.70 (s, C₄and C₅), 20.8 (s, Me) ppm. Elemental analysis calcd. (%)

3

(m, 4H, C₆H₄CF₃), 5.21 (m, 2H, H₃and H₈), 3.81 (d, 2H, J_PH

=

for C₁₈H₂₃O₃Cl₂PRu: C 44.09, H 4.73; found: C 44.00, H 4.81.

10.8 Hz, H₁and H₉), 3.60 (m, 2H, H₅and H₇), 3.13 (br, 2H, H₂(2g): Yield: 0.207 g (84%). IR (KBr): ν = 3188 (br, O-H) cm^-1.

and H₁₀), 2.77 (m, 2H, H₄and H₆), 2.16 (s, 6H, Me) ppm; OH ³¹P{¹H} NMR (CDCl₃): δ = 108.5 (s) ppm. H NMR (CDCl₃): δ =

1

3

signal not observed. ¹³C{¹H} NMR (CDCl₃): δ = 144.5 (d, J_PC

=

4.93 (m, 2H, H₃and H₈), 4.25 (d, 2H, J_PH= 8.2 Hz, H₁and H₉),

1

3

51.6 Hz, C_ipsoof C₆H₄CF₃), 142.7 (d, J_PC= 51.9 Hz, C_ipsoof 3.45 (m, 2H, H₅and H₇), 3.06 (d, 2H, J_PH= 4.8 Hz, H₂and H₁₀),

C₆H₄CF₃), 131.9 (m, CF₃), 130.2 (d, J_PC= 9.8 Hz, CH_orthoor CH_meta2.86 (m, 2H, H₄and H₆), 2.24 (s, 6H, Me), 2.03 (d, 3H, ²J_HP= 9.5

2

of C₆H₄CF₃), 130.0 (d, J_PC= 9.9 Hz, CH_orthoor CH_metaof C₆H₄CF₃), Hz, PMe) 1.91 (d, 3H, J_HP= 9.6 Hz, PMe) ppm; OH signal not

125.6 (s, C₂and C₇), 125.2 (m, C_paraand CH_orthoor CH_metaof observed. ¹³C{¹H} NMR (CDCl₃): δ = 121.0 (s, C₂and C₇), 108.2

2

C₆H₄CF₃), 108.7 (br, C₃and C₆), 66.7 (s, C₁and C₈), 37.2 (s, C₄(d, J_CP= 9.7 Hz, C₃and C₆), 63.4 (d, J_CP= 6.2 Hz, C₁and C₈),

1

and C₅), 21.1 (s, Me) ppm. Elemental analysis calcd. (%) for 36.5 (s, C₄and C₅), 22.2 (d, J_CP= 35.7 Hz, PMe), 20.6 (s, Me),

C₂₄H₂₅F₆Cl₂OPRu: C 44.60, H 3.90; found: C 44.65, H 3.86. (2d): 19.8 (d, ¹J_CP= 41.1 Hz, PMe) ppm. Elemental analysis calcd. (%)

Yield: 0.279 g (81%). IR (KBr): ν = 3020 (br, O-H) cm^-1. ³¹P{¹H} for C₁₂H₂₃Cl₂OPRu: C 37.31, H 6.00; found: C 37.17, H 6.38.

NMR (CDCl₃): δ = 80.9 (s) ppm. H NMR (CDCl₃): δ = 8.00 (m, (2h): Yield: 0.212 g (80%). IR (KBr): ν = 3197 (br, O-H) cm^-1.

1

2H, C₆H₄Me), 7.89 (m, 2H, C₆H₄Me), 7.68 (s, 1H, OH), 7.21 (m, ³¹P{¹H} NMR (CDCl₃): δ = 114.8 (s) ppm. H NMR (CDCl₃): δ =

1

3

4H, C₆H₄Me), 5.13 (m, 2H, H₃and H₈), 3.86 (d, 2H, J_PH= 10.5 5.96 (br, 1H, OH), 4.94 (m, 2H, H₃and H₈), 4.32 (d, 2H, J_PH

Hz, H₁and H₉), 3.54 (m, 2H, H₅and H₇), 3.15 (d, 2H, J_PH= 3.0 7.8 Hz, H₁and H₉), 3.43 (m, 2H, H₅and H₇), 3.10 (d, 2H, J_PH

=

3

Hz, H₂and H₁₀), 2.72 (m, 2H, H₄and H₆), 2.38 (s, 3H, C₆H₄Me), 3.9 Hz, H₂and H₁₀), 2.80 (m, 2H, H₄and H₆), 2.44-2.23 (m, 4H,

2.35 (s, 3H, C₆H₄Me), 2.15 (s, 6H, Me) ppm. ¹³C{¹H} NMR PCH₂CH₃), 2.20 (s, 6H, Me), 1.35-1.23 (m, 6H, PCH₂CH₃) ppm.

4

2

(CDCl₃): δ = 139.9 (d, J_PC= 2.0 Hz, C_paraof C₆H₄Me), 139.6 (d, ¹³C{¹H} NMR (CDCl₃): δ = 121.5 (s, C₂and C₇), 108.3 (d, J_CP

=

⁴J_PC= 2.1 Hz, C_paraof C₆H₄Me), 137.7 (d, J_PC= 55.6 Hz, C_ipsoof 9.3 Hz, C₃and C₆), 62.9 (d, J_CP= 6.2 Hz, C₁and C₈), 36.5 (s, C₄

C₆H₄Me), 136.0 (d, ¹J_PC= 56.1 Hz, C_ipsoof C₆H₄Me), 129.7 (d, J_PCand C₅), 25.5 (d, ¹J_CP= 29.5 Hz, PCH₂CH₃), 22.8 (d, ¹J_CP= 35.3 Hz,

= 9.3 Hz, CH_orthoor CH_metaof C₆H₄Me), 129.5 (d, J_PC= 9.5 Hz, PCH₂CH₃), 20.7 (s, Me), 7.56 (d, ²J_CP= 3.8 Hz, PCH₂CH₃), 7.21 (d,

1

2

CH_orthoor CH_metaof C₆H₄Me), 129.0 (d, J_PC= 10.8 Hz, CH_orthoor J_CP= 6.3 Hz, PCH₂CH₃) ppm. Elemental analysis calcd. (%) for

CH_metaof C₆H₄Me), 128.7 (d, J_PC= 10.7 Hz, CH_orthoor CH_metaof C₁₄H₂₇Cl₂OPRu: C 40.59, H 6.57; found: C 40.47, H 6.60.

C₆H₄Me), 125.0 (s, C₂and C₇), 107.4 (br, C₃and C₆), 67.3 (s, C₁

and C₈), 37.2 (s, C₄and C₅), 21.4, 21.3 and 21.1 (s, C₆H₄Me and

Synthesis of [RuCl₂(η³:η³-C₁₀H₁₆)(PR₂Cl)] (R = Ph (3a), 4-C₆H₄F

Me) ppm. Elemental analysis calcd. (%) for C₂₄H₃₁Cl₂OPRu: C

(3b), 4-C₆H₄CF₃(3c), 4-C₆H₄Me (3d), 4-C₆H₄OMe (3e), 2-Furyl

53.54, H 5.80; found: C 53.60, H 5.88. (2e): Yield: 0.284 g

(3f))

(78%). IR (KBr): ν = 3025 (br, O-H) cm^-1. ³¹P{¹H} NMR (C₆D₆): δ =

80.8 (s) ppm. H NMR (C₆D₆): δ = 8.50 (s, 1H, OH), 8.44-8.25

A purple solution of the dimeric precursor [{RuCl(µ-Cl)(η³:η³-

C₁₀H₁₆)}₂] (1) (0.200 g, 0.32 mmol) in dichloromethane (30 mL)

1

(m, 4H, C₆H₄OMe), 6.83 (m, 4H, C₆H₄OMe), 5.27 (m, 2H, H₃and

3

was treated, at room temperature, with the appropriate

chloro-phosphine ligand (0.70 mmol) for 3 h. The solvent was

then removed under reduced pressure. The resulting yellow

oily residue was washed with hexanes (2 x 5 mL) and diethyl

ether (2 x 5 mL), and dried in vacuo to afford complexes 3a-f as

yellow solids. (3a): Yield: 0.305 g (90%). ³¹P{¹H} NMR (CD₂Cl₂):

H₈), 4.13 (d, 2H, J_PH= 10.5 Hz, H₁and H₉), 3.54 (d, 2H, J_PH

=

3.3 Hz, H₂and H₁₀), 3.32 (s, 3H, C₆H₄OMe), 3.30 (s, 3H,

C₆H₄OMe), 3.19 (m, 2H, H₅and H₇), 2.25 (m, 2H, H₄and H₆),

4

2.17 (s, 6H, Me) ppm. ¹³C{¹H} NMR (C₆D₆): δ = 161.0 (d, J_PC

=

4

2.8 Hz, C_paraof C₆H₄OMe), 160.8 (d, J_PC= 2.7 Hz, C_paraof

C₆H₄OMe), 133.1 (d, ¹J_PC= 59.1 Hz, C_ipsoof C₆H₄OMe), 131.7 (d,

8 | J. Name., 2012, 00, 1-3

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Journal Name

ARTICLE

1

δ = 114.2 (s) ppm. H NMR (CD₂Cl₂): δ = 8.03 (m, 2H, Ph), 7.91 ppm. H NMR (C₆D₆): δ = 8.18 (m, 4H, C₆H₄OMe),_V6_ie._w7_A8_rti(_cm_{le O}, _n4_liH_ne,

3

(m, 2H, Ph), 7.47 (m, 6H, Ph), 5.30 (m, 2H, H₃and H₈), 4.43 (d, C₆H₄OMe), 5.54 (m, 2H, H₃and H₈), 4.53^D(^Od^I,^:2¹⁰H^.1,⁰³J⁹_P^/_H^C=^6D1^T0⁰.²4³⁷H⁵z^D,

2H, J_PH= 10.5 Hz, H₁and H₉), 3.51 (m, 2H, H₅and H₇), 3.27 (d, H₁and H₉), 3.80 (d, 2H, J_PH= 3.9 Hz, H₂and H₁₀), 3.32 (s, 3H,

3

2H, J_PH= 4.2 Hz, H₂and H₁₀), 2.73 (m, 2H, H₄and H₆), 2.23 (s, C₆H₄OMe), 3.31 (s, 3H, C₆H₄OMe), 3.20 (m, 2H, H₅and H₇), 2.30

6H, Me) ppm. ¹³C{¹H} NMR (CD₂Cl₂): δ = 137.2 (d, ¹J_PC= 40.0 Hz, (s, 6H, Me), 2.46 (m, 2H, H₄and H₆) ppm. ¹³C{¹H} NMR (C₆D₆): δ

1

4

C_ipsoof Ph), 136.5 (d, J_PC= 37.8 Hz, C_ipsoof Ph), 133.1 (d, J_PC

=

= 161.7 (d, J_PC= 1.3 Hz, C_paraof C₆H₄OMe), 161.5 (d, J_PC= 1.4

10.4 Hz, CH_orthoor CH_metaof Ph), 132.0 (d, J_PC= 12.1 Hz, CH_orthoHz, C_paraof C₆H₄OMe), 135.4 (d, J_PC= 12.2 Hz, CH_orthoor CH_meta

4

or CH_metaof Ph), 131.0 (d, J_PC= 2.1 Hz, CH_paraof Ph), 130.7 (d, of C₆H₄OMe), 134.4 (d, J_PC= 12.1 Hz, CH_orthoor CH_metaof

⁴J_PC= 1.8 Hz, CH_paraof Ph), 127.8 (d, J_PC= 9.8 Hz, CH_orthoor C₆H₄OMe), 129.5 (d, ¹J_PC= 36.6 Hz, C_ipsoof C₆H₄OMe), 128.7 (d,

CH_metaof Ph), 127.7 (d, J_PC= 9.7 Hz, CH_orthoor CH_metaof Ph), ¹J_PC= 38.6 Hz, C_ipsoof C₆H₄OMe), 126.8 (s, C₂and C₇), 113.3 (d,

127.1 (s, C₂and C₇), 109.7 (d, ²J_PC= 12.7 Hz, C₃and C₆), 69.0 (d, J_PC= 11.1 Hz, CH_orthoor CH_metaof C₆H₄OMe), 113.2 (d, J_PC= 11.1

2

²J_PC= 5.4 Hz, C₁and C₈), 36.7 (s, C₄and C₅), 20.5 (s, Me) ppm. Hz, CH_orthoor CH_metaof C₆H₄OMe), 108.8 (d, J_PC= 12.7 Hz, C₃

2

Elemental analysis calcd. (%) for C₂₂H₂₆Cl₃PRu: C 49.96, H and C₆), 69.6 (d, J_PC= 4.9 Hz, C₁and C₈), 54.7 (s, C₆H₄OMe),

4.96; found: C 50.11, H 4.89. (3b): Yield: 0.300 g (83%). ³¹P{¹H} 36.6 (s, C₄and C₅), 20.7 (s, Me) ppm. Elemental analysis calcd.

NMR (CD₂Cl₂): δ = 113.0 (s) ppm. ¹⁹F{¹H} NMR (CD₂Cl₂): δ = - (%) for C₂₄H₃₀Cl₃O₂PRu: C 48.95, H 5.13; found: C 49.10, H 5.05.

1

108.8 (s), -109.2 (s) ppm. H NMR (CD₂Cl₂): δ = 8.02 (m, 2H, (3f): Yield: 0.296 g (91%). ³¹P{¹H} NMR (CDCl₃): δ = 82.4 (s)

C₆H₄CF₃), 7.92 (m, 2H, C₆H₄CF₃), 7.18 (m, 4H, C₆H₄CF₃), 5.33 (m, ppm. ¹H NMR (CDCl₃): δ = 7.75 (br, 2H, furyl), 7.22 (d, 1H, ³J_HH

=

3

2H, H₃and H₈), 4.28 (d, 2H, J_PH= 10.8 Hz, H₁and H₉), 3.52 (m, 2.7 Hz, furyl), 7.13 (d, 1H, J_HH= 3.0 Hz, furyl), 6.54 (br, 2H,

3

2H, H₅and H₇), 3.27 (d, 2H, J_PH= 4.5 Hz, H₂and H₁₀), 2.73 (m, furyl), 5.33 (m, 2H, H₃and H₈), 4.60 (d, 2H, J_PH= 11.4 Hz, H₁

2H, H₄and H₆), 2.23 (s, 6H, Me) ppm. ¹³C{¹H} NMR (CD₂Cl₂): δ = and H₉), 3.55 (m, 2H, H₅and H₇), 3.45 (d, 2H, J_PH= 4.5 Hz, H₂

3

164.2 (d, J_FC= 253.2 Hz, C_paraof C₆H₄F), 164.1 (d, J_FC= 252.6 and H₁₀), 2.73 (m, 2H, H₄and H₆), 2.23 (s, 6H, Me) ppm. ¹³C{¹H}

1

Hz, C_paraof C₆H₄F), 135.1 (m, CH_orthoor CH_metaof C₆H₄F), 132.9 NMR (CDCl₃): δ = 148.3 (d, J_PC= 62.8 Hz, C of furyl), 148.2 (d,

(d, ¹J_PC= 34.1 Hz, C_ipsoof C₆H₄F), 132.3 (d, ¹J_PC= 39.4 Hz, C_ipsoof J_PC= 65.6 Hz, C of furyl), 147.7 (d, J_PC= 6.4 Hz, CH of furyl),

1

C₆H₄F), 127.3 (s, C₂and C₇), 115.0 (m, CH_orthoor CH_metaof 147.6 (d, J_PC= 6.7 Hz, CH of furyl), 126.7 (s, C₂and C₇), 122.9 (d,

C₆H₄F), 110.0 (d, ²J_PC= 12.7 Hz, C₃and C₆), 69.1 (d, ²J_PC= 4.8 Hz, J_PC= 14.8 Hz, CH of furyl), 122.7 (d, J_PC= 15.0 Hz, CH of furyl),

C₁and C₈), 36.7 (s, C₄and C₅), 20.6 (s, Me) ppm. Elemental 111.1 (d, J_PC= 5.9 Hz, CH of furyl), 111.0 (d, J_PC= 5.8 Hz, CH of

2

analysis calcd. (%) for C₂₂H₂₄Cl₃F₂PRu: C 46.78, H 4.28; found: C furyl), 109.9 (d, J_PC= 14.1 Hz, C₃and C₆), 67.7 (d, ²J_PC= 4.5 Hz,

46.90, H 4.21. (3c): Yield: 0.362 g (85%). ³¹P{¹H} NMR (CD₂Cl₂): C₁and C₈), 36.8 (s, C₄and C₅), 20.8 (s, Me) ppm. Elemental

δ = 111.3 (s) ppm. ¹⁹F{¹H} NMR (CD₂Cl₂): δ = -63.4 (s), -63.5 (s) analysis calcd. (%) for C₁₈H₂₂Cl₃O₂PRu: C 42.49, H 4.36; found:

1

ppm. H NMR (CD₂Cl₂): δ = 8.19 (m, 2H, C₆H₄CF₃), 8.08 (m, 2H, C 42.52, H 4.41.

C₆H₄CF₃), 7.75 (m, 4H, C₆H₄CF₃), 5.35 (m, 2H, H₃and H₈), 4.27

3

(d, 2H, J_PH= 11.1 Hz, H₁and H₉), 3.55 (m, 2H, H₅and H₇), 3.24

Synthesis of [RuCl₂(η³:η³-C₁₀H₁₆)(PR₂OH)] (R = Ph (2a), 4-C₆H₄F

3

(d, 2H, J_PH= 5.1 Hz, H₂and H₁₀), 2.75 (m, 2H, H₄and H₆), 2.23

(2b), 4-C₆H₄CF₃(2c), 4-C₆H₄Me (2d), 4-C₆H₄OMe (2e), 2-Furyl

(s, 6H, Me) ppm. ¹³C{¹H} NMR (CD₂Cl₂): δ = 140.6 (d, ¹J_PC= 30.0

(2f)) from 3a-f

1

Hz, C_ipsoof C₆H₄CF₃), 140.4 (d, J_PC= 31.2 Hz, C_ipsoof C₆H₄CF₃),

To solution of the corresponding complex [RuCl₂(η³:η³-

133.4 (d, J_PC= 11.2 Hz, CH_orthoor CH_metaof C₆H₄CF₃), 132.6 (d,

C₁₀H₁₆)(PR₂Cl)] (3a-f) (0.40 mmol) in tetrahydrofuran (20 mL), 5

J_PC= 9.8 Hz, CH_orthoor CH_metaof C₆H₄CF₃), 131.8 (m, CF₃), 127.5

drops of water were added, and the resulting mixture stirred

(s, C₂and C₇), 124.7 (m, C_paraand CH_orthoor CH_metaof C₆H₄CF₃),

110.8 (d, ²J_PC= 12.6 Hz, C₃and C₆), 68.8 (d, ²J_PC= 4.5 Hz, C₁and

overnight at 50 °C. After this time, the reaction mixture was

allowed to reach the room temperature. Then, it was dried

C₈), 36.8 (s, C₄and C₅), 20.5 (s, Me) ppm. Elemental analysis

with anhydrous MgSO₄, filtered, and evaporated to dryness.

calcd. (%) for C₂₄H₂₄F₆Cl₃PRu: C 43.36, H 3.64; found: C 43.44, H

3.60. (3d): Yield: 0.281 g (79%). ³¹P{¹H} NMR (CD₂Cl₂): δ = 114.9

The resulting yellow oily residue was washed with hexanes (2 x

5 mL) and diethyl ether (2 x 5 mL), and dried in vacuo to afford

complexes 2a-f as yellow solids. (2a): Yield: 0.173 g (85%).

1

(s) ppm. H NMR (CD₂Cl₂): δ = 7.88 (m, 2H, C₆H₄Me), 7.76 (m,

2H, C₆H₄Me), 7.27 (m, 4H, C₆H₄Me), 5.29 (m, 2H, H₃and H₈),

4.31 (d, 2H, ³J_PH= 10.5 Hz, H₁and H₉), 3.50 (m, 2H, H₅and H₇),

(2b): Yield: 0.190 g (87%). (2c): Yield: 0.209 g (81%). (2d): Yield:

3

0.166 g (77%). (2e): Yield: 0.164 g (72%). (2f): Yield: 0.165 g

(84%).

3.27 (d, 2H, J_PH= 5.2 Hz, H₂and H₁₀), 2.70 (m, 2H, H₄and H₆),

2.43 (s, 6H, C₆H₄Me), 2.22 (s, 6H, Me) ppm. ¹³C{¹H} NMR

4

(CD₂Cl₂): δ = 141.5 (d, J_PC= 2.4 Hz, C_paraof C₆H₄Me), 141.2 (d,

⁴J_PC= 1.8 Hz, C_paraof C₆H₄Me), 134.1 (d, J_PC= 33.8 Hz, C_ipsoof

1

General procedure for the catalytic hydration of nitriles with

C₆H₄Me), 133.7 (d, ¹J_PC= 36.2 Hz, C_ipsoof C₆H₄Me), 133.1 (d, J_PC

= 11.9 Hz, CH_orthoor CH_metaof C₆H₄Me), 132.1 (d, J_PC= 10.8 Hz,

CH_orthoor CH_metaof C₆H₄Me), 128.4 (d, J_PC= 11.1 Hz, CH_orthoor

CH_metaof C₆H₄Me), 127.0 (s, C₂and C₇), 109.4 (d, ²J_PC= 12.8 Hz,

[RuCl₂(η³:η³-C₁₀H₁₆)(PMe₂OH)] (2g)

Under inert atmosphere, the corresponding nitrile (1 mmol),

water (3 mL), and the ruthenium complex 2g (0.01-0.05 mmol)

were introduced into a Teflon-capped sealed tube, and the

reaction mixture stirred at 60-100 °C for the indicated time

(see Table 5 and Schemes 5-7). The course of the reaction was

monitored regularly taking samples of ca. 20 μL, which, after

2

C₃and C₆), 69.1 (d, J_PC= 4.8 Hz, C₁and C₈), 36.8 (s, C₄and C₅),

21.2 (s, C₆H₄Me), 20.7 (s, Me) ppm. Elemental analysis calcd.

(%) for C₂₄H₃₀Cl₃PRu: C 51.76, H 5.43; found: C 51.68, H 5.50.

(3e): Yield: 0.328 g (87%). ³¹P{¹H} NMR (C₆D₆): δ = 114.8 (s)

This journal is © The Royal Society of Chemistry 20xx

J. Name., 2013, 00, 1-3 | 9

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Journal Name

extraction with CH₂Cl₂(3 mL), were analyzed by GC (in the case also performed with the program CrysAlis^Proand_Va_ien_{w A}e_rtm_iclp_ei_Or_nic_lina_el

1

of the cyanohydrins the reactions were monitored by H NMR absorption correction was applied using^Dt^Oh^Ie^{: 10}S^.C¹⁰A³L⁹E^/3^C6A^DB^TS⁰²P³A⁷C^5DK

spectroscopy). Once the reaction is completed, two different algorithm as implemented in the program CrysAlis^Pro

.

procedures were applied to isolate the amide product

depending on its solubility. For amides which partially space group determination, structure solution, and

precipitate in the medium, the reaction mixture was cooled at refinement.⁴⁴For 2a

2d/3d and 3f the structures were solved

r.t., or °C in an ice bath, until complete by Patterson interpretation and phase expansion using DIRDIF

precipitation/crystallization of the product. The suspension

and DIRDIF2008 (2d/3d and 3f).⁴⁶For 3c the structure

In all cases the software package WINGX was used for

,

0

45

(2a

)

was then filtered, the solid washed with water (2 x 3 mL) and was solved by a charge flipping iterative algorithm using

hexanes (3 mL) and dried in vacuo. For those amides that do SUPERFLIP.⁴⁷Isotropic least-squares refinements on F²using

48

49

not precipitate, isolation was carried out as follows: After SHELXL97 (2a

)

and SHELXL2014 (2d/3d

,

3c and 3f

)

were

elimination of the water solvent under reduced pressure, the performed. During the final stages of the refinements, all the

crude reaction mixture was pulverized in diethyl ether and the positional and the anisotropic displacement parameters of all

resulting solid filtered, washed and dried in vacuo. In some the non-H atoms were refined. All H atoms (except those

cases additional purification by column chromatography was labeled as H1o) were geometrically located and their

required (silica gel with CH₂Cl₂as the eluent). The identity of coordinates were refined riding on their parent atoms.

the amide products was assessed, in all the cases, by

As commented previously, a mixed crystal of 2d and 3d

comparison of their NMR spectroscopic data with those was measured. SHELXL2014 handles this situation, known as

reported in the literature.

substitutional disorder, without difficulty with the aid of the

PART and FVAR instructions to estimate the ratio of the two

components in the crystal. Once completed the refinement, it

is concluded that 77% of the crystal is formed by compound

2d. The remaining 23% corresponds to compound 3d. An

attempt to solve and refine the crystal in space group P1

confirms that the replacement of the hydroxyl group by a

chlorine atom has no appreciable changes in the rest of the

geometry of the complex; however, statistical descriptors of

the final cycle of the refinement are slightly worse in P1

compared to those obtained in P-1. The atoms H1o of

complexes 2a and 2d/3d were found from the corresponding

difference Fourier maps and included in the refinements with

isotropic displacement parameters. Complex 3c contains two

highly disordered trifluoromethyl groups. Although

SHELXL2014 provides two possible sites for each of the

fluorine atoms, the anisotropic motion of the atoms on a single

Recycling of complex [RuCl₂(η³:η³-C₁₀H₁₆)(PMe₂OH)] (2g)

Under inert atmosphere, pentafluorobenzonitrile (0.193 g, 1

mmol), water (3 mL), and complex 2g (0.0038 g, 0.01 mmol)

were introduced into a Teflon-capped sealed tube, and the

reaction mixture stirred at 60 °C for 30 min. After this time, a

sample of ca. 20 μL was taken and, after extraction with CH₂Cl₂

(3 mL), analyzed by GC to determine the conversion of the

substrate. The reaction mixture was then cooled at 0 °C in an

ice bath until complete crystallization of the amide formed.

The suspension was filtered and pentafluorobenzonitrile

(0.193 g, 1 mmol) added to the aqueous filtrate containing 2g

.

The resulting mixture was introduced into a Teflon-capped

sealed tube, and stirred at 60 °C for 30 min. The same

procedure was repeated for 10 times.

position leads to a better description of this positional

2

disorder. The function minimized was

[

(F_o

-

X-ray crystal structure determination of compounds 2a,

2d/3d, 3c, 3f

2 2

2 2 1/2

2

F_c) /(F_o) ] where

values are collected in Table 6) with



= 1/[²(F_o) + (aP)²+ bP] (a and b

2



(F_o) from counting

2

Crystals suitable for X-ray diffraction analysis were obtained in

all the cases by slow diffusion of hexanes into a saturated

solution of the complex in dichloromethane. The most relevant

statistics and P = (Max(F_o, 0) + 2F_c)/3. Atomic scattering

factors were taken from the International Tables for X-Ray

Crystallography, Volume C.⁵⁰Geometrical calculations related

to the centroids C^*and C^**were made with PARST.⁵¹The

crystallographic plots were made with ORTEP-3.⁴⁴

crystal and refinement data are collected in Table 6. For 2a

,

data collection was performed with an Oxford Diffraction

Xcalibur single-crystal diffractometer with a Ruby detector

using Mo-Kα radiation (λ = 0.7107 Å). Images were collected at

a fixed crystal-to-detector distance of 55 mm using the

Acknowledgements

oscillation method with 1.00

time per image. In the case of 2d/3d

°

oscillation and 15.0 s exposure

3c and 3f, data

This work was supported by the Spanish MINECO (project

CTQ2013-40591-P and CTQ2014-51912-REDC) and the

Gobierno del Principado de Asturias (project GRUPIN14-006).

E.T.-M. and J.F. thank MECD, MINECO and ESF for the award of

a FPU fellowship and a Juan de la Cierva contract (IJCI-2014-

19174), respectively.

,

collections were performed with a Rigaku-Oxford Diffraction

Xcalibur Onyx Nova single-crystal diffractometer using Cu-Kα

radiation (λ = 1.5418 Å). Images were collected at a fixed

crystal-to-detector distance of 62 mm using the oscillation

method with 1.00

° oscillation and 15.0-40.0 s variable

exposure time per image for 2d/3d, 1.5-3.5 s for 3c, and 2.5-

12.5 s for 3f. Data collection strategy was calculated with

program CrysAlis^{Pro 43}

. Data reduction and cell refinement were

10 | J. Name., 2012, 00, 1-3

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View Article Online

DOI: 10.1039/C6DT02375D

Table 6 Crystal data and structure refinement for compounds 2a, 2d/3d, 3c and 3f.

2a

2d/3d

3c

3f

Empirical formula

C₂₂H₂₇Cl₂OPRu

510.38

293(2)

C₂₄H_30.77Cl_2.23O_0.77PRu

542.67

293(2)

1.54184

Triclinic

C₂₄H₂₄F₆Cl₃PRu

664.82

293(2)

1.54184

Monoclinic

C₁₈H₂₂Cl₃O₂PRu

508.74

298(2)

1.54184

Triclinic

Formula weight

Temperature/K

Wavelength/Å

Crystal system

Space group

Crystal size/mm

a/Å

b/Å

c/Å

α (ᵒ)

β (ᵒ)

0.71070

Monoclinic

P2₁/c

0.121 x 0.095 x 0.077

8.9441(1)

14.5843(2)

16.6608(2)

90

96.085(1)

90

4

2161.05(5)

1.569

P-1

P2₁/n

P-1

0.160 x 0.110 x 0.060

9.7474(2)

10.6446(3)

12.2667(4)

90.845(2)

108.020(2)

97.486(2)

2

0.260 x 0.200 x 0.030

11.1019(1)

19.5638(2)

11.8945(1)

90

100.485(1)

90

0.180 x 0.120 x 0.020

8.4372(5)

10.1173(6)

12.3447(6)

96.948(5)

105.301(5)

100.354(5)

2

γ (ᵒ)

Z

4

Volume/Å³

Calculated density/g cm^-3

µ/mm^-1

1197.98(6)

1.504

8.299

2540.29(4)

1.738

9.016

983.1(1)

1.717

11.045

1.057

F(000)

θ range/°

Index ranges

1040

556

1328

512

6.63-89.80

-10 ≤ h ≤ 11

-18 ≤ k ≤ 18

-21 ≤ l ≤ 21

99.8%

16714

4936 (R_int= 0.0315)

248/1

3.80-69.72

-11 ≤ h ≤ 11

-12 ≤ k ≤ 12

-14 ≤ l ≤ 14

98.7%

23573

4463 (R_int= 0.0232)

280/0

4.40-69.46

-13 ≤ h ≤ 13

-20 ≤ k ≤ 23

-13 ≤ l ≤ 14

98.1%

3.77-69.52

-8 ≤ h ≤ 10

-11 ≤ k ≤ 12

-14 ≤ l ≤ 10

97.3%

9114

3593 (R_int= 0.0612)

226/0

Completeness to θ_max

No. of reflns. collected

No. of unique reflns.

No. of parameters/restraints

Refinement method

Goodness-of-fit on F²

Weight function (a, b)

R₁[I > 2σ(I)]^a

12010

4679 (R_int= 0.0359)

316/0

Full-matrix least-squares on F²

1.026

0.0451, 0.0000

0.0280

0.0751

1.088

0.0526, 0.6359

0.0341

0.0940

1.028

0.0596, 3.4297

0.0396

0.1037

1.076

0.1294, 0.1720

0.0624

0.1808

wR₂[I > 2σ(I)]^a

R₁(all data)

0.0379

0.0772

0.436, -0.406

0.0418

0.1004

0.387, -0.660

0.0437

0.1084

0.938, -0.818

0.0678

0.1906

1.004, -1.524

R₂(all data)

Largest diff. peak and hole/e Å^-3

^aR₁= ∑(|F_o|-|F_c|)/∑|F_o|; wR₂= {∑[w(F_o²-F_c²)²]/∑[w(F_o²)²]}^1/2

Verlag, Berlin, 2004; (c) Ruthenium in Catalysis, eds. C.

Bruneau and P. H. Dixneuf, Springer-Verlag, Berlin, 2014.

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6

Notes and references

Warratz, D. Gelman, S. J. Garden and L. Ackermann, Chem.

Eur. J., 2016, 22, 1248; (c) L. V. Graux, M. Giorgi, G. Buono

and H. Clavier, Dalton Trans., 2016, 45, 6491.

L. V. Graux, M. Giorgi, G. Buono and H. Clavier,

Organometallics, 2015, 34, 1864.

E. Rafter, T. Gutmann, F. Löw, G. Buntkowsky, K. Philippot, B.

Chaudret, P. W. N. M. van Leeuwen, Catal. Sci. Technol.,

2013, 3, 595.

(a) T. Oshiki and M. Muranaka, PCT Int. Appl., WO

2012/017966; (b) S. M. M. Knapp, T. J. Sherbow, R. B. Yelle, J.

J. Juliette and D. R. Tyler, Organometallics, 2013, 32, 3744;

(c) E. Tomás-Mendivil, V. Cadierno, M. I. Menéndez and R.

López, Chem. Eur. J., 2015, 21, 16874.

1

For reviews, see: (a) N. V. Dubrovina and A. Börner, Angew.

Chem. Int. Ed., 2004, 43, 5883; (b) L. Ackermann, Synthesis,

2006, 1557; (c) L. Ackermann, Isr. J. Chem., 2010, 50, 652; (d)

T. M. Shaikh, C.-M. Weng and F. E. Hong, Coord. Chem. Rev.,

2012, 256, 771; (e) T. Achard, Chimia, 2016, 70, 8.

7

8

2

3

J. Chatt and B. T. Heaton, J. Chem. Soc. A, 1968, 2745.

For reviews, see: (a) D. M. Roundhill, R. F. Sperline and W. B.

Beaulieu, Coord. Chem. Rev., 1978, 26, 263; (b) B. Walther,

Coord. Chem. Rev., 1984, 60, 67; (c) T. Appleby and J. D.

Woollins, Coord. Chem. Rev., 2002, 235, 121.

For studies and discussions of the factors affecting this

equilibrium, see: (a) H. J. Brass, R. A. Di Prete, J. O. Edwards,

R. G. Lawler, R. Curci and G. Modena, Tetrahedron, 1970, 26

9

4

,

10 E. Tomás-Mendivil, L. Menéndez-Rodríguez, J. Francos, P.

Crochet and V. Cadierno, RSC Adv., 2014, , 63466.

4555; (b) B. Hoge, S. Neufeind, S. Hettel, W. Wiebe and C.

Thösen, J. Organomet. Chem., 2005, 690, 2382; (c) B. Hoge,

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Wiley-VCH, Weinheim, 2004; (b) Ruthenium Catalysts and

Fine Chemistry, eds. C. Bruneau and P. H. Dixneuf, Springer-

4

11 In this context, the phosphinous acid-platinum(II) complex

[PtH{(PMe₂O)₂H}(PMe₂OH)] (Parkins catalyst) merits to be

mentioned since it is one of the most versatile catalysts

currently available for the hydration of C≡N bonds: (a) T.

Ghaffar and A. W. Parkins, Tetrahedron Lett., 1995, 36, 8657;

(b) T. Ghaffar and A. W. Parkins, J. Mol. Catal. A: Chem.,

2000, 160, 249; (c) For a review on the synthetic applications

5

of this complex, see: V. Cadierno, Appl. Sci., 2015, 5, 380.

J. Name., 2013, 00, 1-3 | 11

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ARTICLE

Journal Name

12 For reviews on this catalytic transformation, see: (a) V. Y.

Kukushkin and A. J. L. Pombeiro, Chem. Rev., 2002, 102

R. García-Álvarez, S. E. García-Garrido, J. Díez, P_V._ieC_wro_Arc_tih_cle_et_Oa_nln_ind_e

V. Cadierno, J. Organomet. Chem., _D2_O0_I:1₁3₀,_.107₃2₉7_/C, ₆1_D;_T0(₂d₃)₇₅L_D.

Menéndez-Rodríguez, E. Tomás-Mendivil, J. Francos, P.

Crochet, V. Cadierno, A. Antiñolo, R. Fernández-Galán and F.

Carrillo-Hermosilla, Organometallics, 2015, 34, 2796.

23 (a) G. A. Jeffrey, in An Introduction to Hydrogen Bonding,

Oxford University Press, Oxford, 1997; (b) T. Steiner, Angew.

Chem. Int. Ed., 2002, 41, 48.

,

1771; (b) V. Y. Kukushkin and A. J. L. Pombeiro, Inorg. Chim.

Acta, 2005, 358, 1; (c) T. J. Ahmed, S. M. M. Knapp and D. R.

Tyler, Coord. Chem. Rev., 2011, 255, 949; (d) R. García-

Álvarez, P. Crochet and V. Cadierno, Green Chem., 2013, 15

46; (e) R. García-Álvarez, J. Francos, E. Tomás-Mendivil, P.

Crochet and V. Cadierno, J. Organomet. Chem., 2014, 771

,

93; (f) P. Crochet and V. Cadierno, Top. Organomet. Chem., 24 Metal-bound chlorine atoms are well-known H-bond

2014, 48, 81.

acceptors: G. Aullón, D. Bellamy, L. Brammer, E. A. Bruton

and A. G. Orpen, Chem. Commun., 1998, 653.

13 (a) V. Cadierno, J. Francos and J. Gimeno, Chem. Eur. J., 2008,

14, 6601; (b) R. García-Álvarez, J. Díez, P. Crochet and V. 25 F. H. Allen, O. Kennard, D. G. Watson, L. Brammer, A, G,

Cadierno, Organometallics, 2010, 29, 3955; (c) R. García-

Orpen and R. Taylor, J. Chem. Soc., Perkin Trans. 2, 1987, S1.

Álvarez, J. Díez, P. Crochet and V. Cadierno, Organometallics, 26 See references 13g and 20, and: (a) Í. Ferrer, J. Rich, X.

2011, 30, 5442; (d) R. García-Álvarez, J. Francos, P. Crochet

and V. Cadierno, Tetrahedron Lett., 2011, 52, 4218; (e) M. L.

Buil, V. Cadierno, M. A. Esteruelas, J. Gimeno, J. Herrero, S.

Fontrodona, M. Rodríguez and I. Romero, Dalton Trans.,

2013, 42, 13461; (b) Í. Ferrer, X. Fontrodona, M. Rodríguez

and I. Romero, Dalton Trans., 2016, 45, 3163.

Izquierdo and E. Oñate, Organometallics, 2012, 31, 6861; (f) 27 Very recently, a Ru-NHC complex active at r.t., and featuring

R. García-Álvarez, S. E. García-Garrido, J. Díez, P. Crochet and

V. Cadierno, Eur. J. Inorg. Chem., 2012, 4218; (g) R. García-

Álvarez, M. Zablocka, P. Crochet, C. Duhayon, J.-P. Majoral

TOFs up to 49 h^-1, has been described. However, the use of

an organic co-solvent was needed: M. Nirmala, G. Saranya

and P. Viswanathamurthi, Inorg. Chim. Acta, 2016, 442, 134.

and V. Cadierno, Green Chem., 2013, 15, 2447; (h) E. Tomás- 28 In our previous study with phosphinous acid-Ru(II)

Mendivil, R. García-Álvarez, C. Vidal, P. Crochet and V. complexes of type (Fig. 1), we found that 24 h were

Cadierno, ACS Catal., 2014, , 1901. required to convert quantitatively acetonitrile into

acetamide employing mol% of

[RuCl₂(η⁶-p-

A

4

14 V. Cadierno, J. Díez, J. Francos and J. Gimeno, Chem. Eur. J.,

2010, 16, 9808.

1

cymene)(PMe₂OH)] at 60 °C in pure water. This fact indicates

the superior performance of the Ru(IV) complex 2g, which

may be reasoned in terms of the more effective activation of

C≡N bond upon coordination to the stronger Lewis acid

Ru(IV) center.

15 To

the

best

of

our

knowledge,

complexes

[Cp*RuHX(PPh₂OH){P(=O)Ph₂}] (X = H, Cl) are the only

examples of Ru(IV)-PA complexes quoted in the literature: R.

Torres-Lubián, M. J. Rosales-Hoz, A. M. Arif, R. D. Ernst and

M. A. Paz-Sandoval, J. Organomet. Chem., 1999, 585, 68.

16 E. Tomás-Mendivil, F. J. Suárez, J. Díez and V. Cadierno,

Chem. Commun., 2014, 50, 9661.

29 See, for example: (a) S. Hakimian, A. Cheng-Hakimian, C. D.

Anderson and J. W. Miller, Expert Opin. Pharmacother.,

2007,

2010, 44, 658; (c) G. Coppola, Neuropsychiatr. Dis. Treat.,

2011, , 399; (d) F. M. C. Besag, Expert Opin. Pharmacother.,

8, 1931; (b) C. S. Wisneiwski, Ann. Pharmacother.,

17 For reviews covering the chemistry of dimer [{RuCl(µ-

Cl)(η³:η³-C₁₀H₁₆)}₂] (

1

), see: (a) V. Cadierno, P. Crochet, S. E.

7

García-Garrido and J. Gimeno, Curr. Org. Chem., 2006, 10

,

2011, 12, 801; (e) M. E. Lemmon and E. H. Kossoff, Curr.

Treat. Options Neurol., 2013, 15, 519; (f) D. Ott, S. Borukhova

and V. Hessel, Green Chem., 2016, 18, 1096.

165; (b) C. Bruneau and M. Achard, Coord. Chem. Rev., 2012,

256, 525; (c) J. Francos, S. E. García-Garrido, J. García-

Álvarez, P. Crochet, J. Gimeno and V. Cadierno, Inorg. Chim. 30 See, for example: (a) R. G. W. Spickett, A. Vega, J. Prieto, J.

Acta, 2016, DOI: 10.1016/j.ica.2016.05.012.

Moragues, M. Marquez and D. J. Roberts, Eur. J. Med. Chem.,

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Topai, G. Zampella, V. Russo, N. D. Bello, G. Nano, L. Nicolini,

18 In no case O-coordination of the SPOs to the [RuCl₂(η³:η³-

C₁₀H₁₆)] fragment was observed. For examples of ruthenium

complexes showing this rare coordination mode, see

reference 7.

P. Fantucci, S. Florio and F. Colotta, J. Med. Chem., 2005, 48

,

19 See reference 2 and: (a) C. S. Kraihanzel and C. M. Bartish, J.

Am. Chem. Soc., 1972, 94, 3572; (b) D. E. Berry, K. A.

Beveridge, G. W. Bushnell and K. R. Dixon, Can. J. Chem.,

1985, 63, 2949; (c) D. E. Berry, K. A. Beveridge, G. W.

4312; (c) G. D. Yadav and J. L. Ceasar, Org. Process Res. Dev.,

2008, 12, 740; (d) A. K. Jain, M. G. Gund, D. C. Desai, N.

Borhade, S. P. Senthilkumar, M. Dhiman, N. K. Mangu, S. V.

Mali, N. P. Dubash, S. Halder and A. Satyam, Bioorg. Chem.,

2013, 49, 40.

Bushnell, K. R. Dixon and A. Pidcock, Can. J. Chem., 1986, 64

,

343; (d) K. Diemert, A. Hinz and D. Lorenzen, J. Organomet. 31 For examples of catalytic systems able to monohydrate

Chem., 1990, 393, 379; (e) M. Alonso, M. A. Alvarez, M. E.

García, D. García-Vivó and M. A. Ruiz, Inorg. Chem., 2010, 49

selectively dinitriles, see: (a) C. Crisóstomo, M. G. Crestani

and J. J. García, J. Mol. Catal. A: Chem., 2007, 266, 139; (b) S.

E. García-Garrido, J. Francos, V. Cadierno, J.-M. Basset and V.

,

8962; (f) V. Nesterov, S. Schwieger, G. Schnakenburg, S.

Grimme and R. Streubel, Organometallics, 2012, 31, 3457.

20 R. González-Fernández, P. J. González-Liste, J. Borge, P.

Polshettiwar, ChemSusChem, 2011,

4, 104; (c) X. Xin, D.

Xiang, J. Yang, Q. Zhang, F. Zhuo and D. Dong, J. Org. Chem.,

2013, 78, 11956.

Crochet and V. Cadierno, Catal. Sci. Technol., 2016, 6, 4398.

21 In complete agreement with the absence of reactivity of 32 See, for example: (a) T. J. Ahmed, B. R. Fox, S. M. M. Knapp,

t

dimer

1

with the bulky SPOs Bu₂P(=O)H and Cy₂P(=O)H, all

R. B. Yelle and J. J. Juliette, Inorg. Chem., 2009, 48, 7828; (b)

attempts to generate complexes [RuCl₂(η³:η³-C₁₀H₁₆)(PR₂Cl)]

(R = Bu, Cy) from the reaction of

T. J. Sherbow, E. L. Downs, R. I. Sayler, J. J. Razink, J. J.

t

1

with the corresponding

Juliette and D. R. Tyler, ACS Catal., 2014, 4, 3096.

chlorophosphine PR₂Cl also failed. This highlights the steric 33 Only two ruthenium complexes capable of hydrate

constraints imposed by the [RuCl₂(η³:η³-C₁₀H₁₆)] fragment.

22 See, for example: (a) V. Cadierno, P. Crochet, J. Díez, J.

García-Álvarez, S. E. García-Garrido, J. Gimeno, S. García-

Granda and M. A. Rodríguez, Inorg. Chem., 2003, 42, 3293;

(b) V. Cadierno, P. Crochet, J. Díez, J. García-Álvarez, S. E.

García-Garrido, S. García-Granda, J. Gimeno and M. A.

Rodríguez, Dalton Trans., 2003, 3240; (c) E. Tomás-Mendivil,

cyanohydrins, namely [RuCl₂(η⁶-p-cymene)(PMe₂OH)] (of

type

A

in Fig. 1) and [RuCl₂(η⁶-p-cymene){P(NMe₂)₃}] have

been previously described. Under identical reaction

conditions to those employed herein, the former was able to

convert lactonitrile into 2-hydroxypropanamide in 94% yield

(by ¹H NMR) after 17.5 h, and the latter in > 99% (by ¹H

NMR) after 112 h. See ref. 9b and: S. M. M. Knapp, T. J.

12 | J. Name., 2012, 00, 1-3

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ARTICLE

Sherbow, R. B. Yelle, L. N. Zakharov, J. J. Juliette and D. R.

Tyler, Organometallics, 2013, 32, 824.

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DOI: 10.1039/C6DT02375D

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The preparation of bis(allyl)-Ru(IV) complexes with phosphinous acid ligands is

presented, as well as their application as catalysts in the base-free hydration of

organonitriles in water.

Article Doi

Bis(allyl)-ruthenium(IV) complexes with phosphinous acid ligands as catalysts for nitrile hydration reactions

DOI: 10.1039/c6dt02375d

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