ES2395649B2 - SYNTHESIS OF PALADIO COMPLEXES (0) AND NICKEL (0) WITH N-HETEROCYCLIC AND STYRENE CARBENE LIGANDS - Google Patents

Abstract

The invention relates to the synthesis of complexes of nickel (0) and palladium (0) with N-heterocyclic carbene ligands IPr (1,3-bis(2,6-diisopropylphenyl)-imidazole-2-ylidene) and SIPr (1,3-bis(2,6-diisopropylphenyl)-4,5-dihydroimidazole-2-ylidene) and styrene.

Description

Synthesis of palladium (0) and nickel (0) complexes with n-heterocyclic carbine ligands and styrene.

FIELD OF THE INVENTION

The present invention generally falls within the field of organometallic chemistry and catalysis, and in particular describes the synthesis of palladium (0) and nickel (0) complexes containing N-heterocyclic carbine-type ligands in their coordination sphere. and styrene.

STATE OF THE PREVIOUS TECHNIQUE

Transition metal complexes have been widely used in organic synthesis, both in catalytic and stoichiometric reactions (Tsuji J Transition Metal Reagents and Catalysts: Innovations in Organic Synthesis. Wiley, New York, 2002). The elements of group 10 are the most used in both industrial and laboratory-scale processes (Abel, E. WStone, FGA Wilkinson, G. Eds. Comprehensive Organometallic Chemistry II; Pergamon: New York, 1995; Vol. 9. Morris Bullock, R. Catalysis without Precious Metals, Wiley-VCH, Weinheim, 2010. Negishi, E.-i. de Meijere, A. Handbook of Organopalladium Chemistry for Organic Synthesis, Wiley-Interscience, New York, 2002)

On the other hand, it is worth highlighting the increase in the number of catalytic applications of these metal complexes with N-heterocyclic carbine-type ligands (NHC) in the last fifteen years (Glorius, F. N-Heterocyclic Carbenes in Transition Metal Catalysis - Topics in Organometallic Chemistry, Springer, Heidelberg, 2007). Although for many of these processes it has been proposed that the catalytically active species is a metal complex in a state of zero oxidation, the bibliographic precedents on the use of well-defined catalytic precursors of the type (NHC) M (0) (M = Ni and Pd) are scarce (Díez-González, S .; Marion, N .; Nolan, SP Chem. Rev. 2009, 109, 3612–3676. Fantasia, S .; Nolan, SP Chem. Eur. J. 2008 , 14, 6987-6993). The interest in obtaining well-defined (NHC) palladium (0) and (NHC) nickel (0) complexes lies primarily in preventing the in situ reduction of a metal precursor in the +2 oxidation state (for example , Pd (OAc) 2 or Ni (acac) 2) or from catalytic precursors of Ni (0) or Pd (0) (for example, in the case of nickel Ni (cod) 2, cod = 1,5 octactadiene, and in the case of palladium, Pd (dba) 2, dba = dibenzylidenacetone), these procedures that can generate inactive species, especially metallic palladium and nickel.

Since in a good number of processes catalyzed by species "NHC-M (0)" (M = Pd and Ni) the intervention of monocoordinated intermediates of Ni (0) and Pd (0) has been proposed as the catalytically active species , the use of a labile ligand L in a complex (NHC) MLn could favor the availability of "(NHC) M" units in solution, while ensuring accurate 1: 1 stoichiometry between the NHC ligand and the metal M ( Glorius, F. N-Heterocyclic Carbenes in Transition Metal Catalysis- Topics in Organometallic Chemistry, Springer, Heidelberg, 2007, p. 15). There are few examples of synthesized complexes of the type (NHC) M (L) 2 where L = olefin and M = Ni, Pd, although some of them have already been used in catalytic processes. Thus, for example, the use of palladium (0) (dvds) (dvds = 2,2-1,1,3,3-tetramethyl-1,3-divinyl-disiloxane) (Jackstell, R) complexes has been described. .; Andreu, MG; Frisch, A .; Selvakumar, K .; Zapf, A .; Klein, H .; Spannenberg, A .; Briel, O .; Karch, R .; Angew. Chem., Int. Ed. 2002, 41, 986–989 Jackstell, R .; Frisch, A .; Beller, M .; Röttger, D .; Malaun, M .; Bildstein, BJ Mol. Catal. A: Chem. 2002, 185, 105– 112. Behr, A .; Becker, M .; Beckmann, T .; Johnen, L .; Leschinski, J .; Reyer, S. Angew. Chem. Int. Ed. 2009, 48, 3598-3614. Torrente-Murciano , L .: Lapkin, A .; Nielsen, DJ; Fallis, I .; Cavell, KJ Green Chem. 2010, 12, 866–869) in dietary telomerization reactions. The complexes (IMes) Pd (olefin) 2 [olefin = maleic anhydride (ma), dimethyl fumarate (dmfu), quinone); IMes = 1,3-dimesitylimidazol-2-ylidene] have been used in alkyne hydrogenation reactions (Sprengers, JW; Wassenaar, J .; Clement, ND; Cavell, KJ; Elsevier CJ Angew. Chem. Int. Ed. 2005 , 44, 2026-2029). Finally, it has been described that the (IMes) palladium (0) complexes with quinone ligands act as very efficient catalysts in cross-coupling reactions of diaryldiazonium salts with olefins (Selvakumar, K .; Zapf, A .; Spannenberg, A .; Beller, M. Chem Eur. J. 2002, 8, 3901-3906). In the case of nickel, complexes similar to those described by Cavell et al. (Clement, ND; Cavell, KJ; Ooi, L. Organometallics 2006, 25, 4155 4165), of the type (NHC) Ni (dmfu) have been shown 2 have a good catalytic activity in the oxidation of secondary alcohols (Berini, C .; Winkelmann, OH; Otten, J .; Vicic,

GIVES.; Navarro, O. Chem. Eur. J. 2010, 16, 6857-6860).

The synthesis methods described in the state of the art for complexes of the type (NHC) M (olefin) 2 (M = Ni and Pd) are suitable for obtaining reasonable amounts thereof, however, the catalysts thus obtained are poor. assets. There is therefore a need to provide new processes for obtaining these complexes that give rise to more active catalysts.

DESCRIPTION OF THE INVENTION

Thus, in a first aspect, the present invention provides a compound of general formula I

ES 2 395 649 Al

where M is a metal in oxidation state 0, selected from Pd or Ni NHC is an N-heterocyclic carbine ligand,

In a more particular embodiment, the compound of general formula I is (NHC) Pd (styrene) 2.

In a more particular embodiment of the present invention, the N-heterocyclic carbine ligand NHC is 1,3bis (2,6-diisopropylphenyl) -imidazol-2-ylidene, in another more particular embodiment, the N-heterocyclic carbine ligand NHC is 1,3-bis (2,6-diisopropylphenyl) -4,5-dihydroimidazol-2-ylidene.

In a more particular embodiment, the compound of general formula I is (NHC) Ni (styrene) 2.

In a more particular embodiment of the present invention, the N-heterocyclic carbine ligand NHC is 1,3bis (2,6-diisopropylphenyl) -imidazol-2-ylidene, in another more particular embodiment, the N-heterocyclic carbine ligand. NHC is 1,3-bis (2,6-diisopropylphenyl) -4,5-dihydroimidazol-2-ylidene.

In a second aspect, the present invention relates to a method of synthesizing compounds of formula

general I (compound of the present invention) where

20 M is a metal in oxidation state 0, selected from Pd or Ni, NHC is an N-heterocyclic carbine ligand, selected from 1,3-bis (2,6-diisopropylphenyl) -imidazol-2-ylidene or 1 , 3-bis (2,6-diisopropylphenyl) -4,5-dihydroimidazol-2-ylidene, characterized in that the compound of general formula I is synthesized from a metal-M complex together with an excess of styrene and a base, under an inert atmosphere of nitrogen, free of O2, and at room temperature.

In a more particular embodiment, the present invention relates to a method of synthesis of compounds of general formula I according to the present invention, where M is Pd, the metal-M complex is NHC-Pd (allyl) Cl, the base is potassium tertbutoxide in isopropanol, in a more particular embodiment the NHC ligand is 1,3-bis (2,6-diisopropylphenyl) -imidazol-2-ylidene. In another more particular embodiment the NHC ligand is 1,3-bis (2,6

Diisopropylphenyl) -4,5-dihydroimidazol-2-ylidene.

In a more particular embodiment, the present invention relates to a method of synthesis of compounds of general formula I according to the present invention, where M is Ni, the metal-M complex is bis (1,5-cyclooctadiene) nickel (0), in THF as a reaction medium and comprises the addition of NHC. In one more embodiment

In particular, the NHC ligand is 1,3-bis (2,6-diisopropylphenyl) -imidazol-2-ylidene. In another more particular embodiment, the NHC ligand is 1,3-bis (2,6-diisopropylphenyl) -4,5-dihydroimidazol-2-ylidene.

In a third aspect, the present invention relates to the use of the compound of general formula I (compound of the present invention) as a catalyst. 40 DETAILED DESCRIPTION OF THE INVENTION.

All reactions and manipulations were carried out under an inert atmosphere of nitrogen, free of oxygen, using Schlenk techniques. The solvents were dried and stored under an inert atmosphere before use. Imidazolium salts, IPr · HCl (1,3-bis (2,6-diisopropylphenyl) imidazolium chloride) SIPr · HCl (1,3-bis (2,6-diisopropylphenyl) -4,5-dihydroimidazolium chloride) , the corresponding carbenes, IPr and SIPr (Arduengo, III, AJ; Krafczyk, R .; and Schmutzler, R .; Craig, HA; Goerlich, JR; Marshall, WJ; Unverzagt, M. Tetrahedron 1999, 55, 14523-14534 ), and the complexes of (IPr) Pd (allyl) Cl and (SIPr) Pd (allyl) Cl (Viciu, MS; Germaneau, RF; Navarro-Fernandez, O .; Stevens, ED; Nolan, SP Organometallics 2002, 21 , 5470-5472. (NHC = IPr and SIPr) were synthesized

50 following the procedures described in the bibliography. Ni (cod) 2 was obtained commercially.

ES 2 395 649 Al

The synthesis methods described in the following examples, resulted in the production of tricoordinated nickel and palladium complexes with 16-electron NHC and styrene ligands, where the metal was in a state of zero oxidation.

5 These complexes were stable, under normal conditions, against water, when dissolved in a wide variety of organic solvents such as aromatic hydrocarbons, halogenated hydrocarbons, ethers, aliphatic hydrocarbons, alcohols, and mixtures thereof. The use of the reactions described in the examples did not imply any decomposition of the compounds obtained by them. In addition, they resulted in the isolation of the (NHC) M (styrene) 2 (M = Ni, Pd) complexes with

10 yields greater than 90% and with sufficient purity to be used without the need for any further purification process.

Example 1: Synthesis of complexes (NHC) Pd (styrene) 2

NHC = IPr, SIPr IPr SIPr

The palladium (0) complexes represented above were synthesized from the corresponding palladium (II) allyl compounds, (NHC) Pd (allyl) Cl, which are very stable. As shown in scheme 1, this procedure allowed to synthesize the mentioned styrene adducts without the need to use

20 unstable starting and carrying out the reactions at room temperature.

Cl

KOtBu NHC Pd + excess

NHC Pd iPrOH

temp. amb. 20 min

Scheme 1: synthesis of compounds (NHC) Pd (styrene) 2

The synthesis of compounds (NHC) Pd (styrene) 2 included the preparation of the following palladium complexes (0) with 2 coordinated styrene molecules and an N-heterocyclic carbine ligand (NHC = IPr (1,3-bis (2) , 6-diisopropylphenyl) imidazol-2-ylidene) or SIPr (1,3-bis (2,6-diisopropylphenyl) -4,5-dihydroimidazol-2-ylidene).

Preparation of the complexes (NHC) Pd (styrene) 2 (NHC = IPr and SIPr):

The two complexes (NHC) Pd (styrene) 2 with NHC = IPr and NHC = SIPr, were synthesized following the same procedure. As an example, the synthesis ¡of (IPr) Pd (styrene) 2 is shown.

On a solution of 1.05 g (1.50 mmol) of (IPr) Pd (allyl) Cl and 0.185 g (1.65 mmol) of KOtBu in isopropanol (20 mL) 0.8 mL (6.98 mmol) of styrene was added, a precipitate appearing almost immediately White color.

After 15 min of reaction, 2mL of water was added. The solid obtained was filtered off, washed twice with 10 mL of iPrOH and dried in vacuo. The IPrPd (styrene) 2 complex was isolated as a white crystalline solid in 85% yield (0.84 g, 1.28 mmol).

The spectroscopic data for (IPr) Pd (styrene) 2 were as follows: IR (nujol): v (C = C) = 1505 cm-1. 1H NMR 40 (400 MHz, -40 ° C, toluene-d8) 8 1.05 (d, J = 6.8 Hz, 6H, CH (CH3) 2), 1.07 (d, J = 7.1 Hz, 6H, CH (CH3) 2) , 1.16 (d, J =

6.5 Hz, 6H, CH (CH3) 2), 1.40 (d, J = 6.6 Hz, 6H, CH (CH3) 2), 2.83 (m, 2H, CH (CH3) 2), 2.94, (d, J = 8.9 Hz, 2H, CH2 olefin), 3.07 (d, J = 12.4 Hz, 2H, CH2 olefin), 3.43 (m, 2H, CH (CH3) 2), 3.75 (dd, J = 9.3 Hz, J = 12.0 Hz , 2H CH olefin), 6.67 (s, 2H aromatic styrene). 13C NMR (100 MHz, -40 ° C, toluene-d8) 8 22.31 (s, CH (CH3) 2), 22.84 (CH (CH3) 2),

25.28 (CH (CH3) 2), 27.21 (CH (CH3) 2), 28.32 (CH (CH3) 2), 28.93 (s, CH (CH3) 2), 53.01 (s, CH2 olefin), 74.66 (CH 45 olefin), 124.0 (broad s, CH imid), 123.28 (s, 4C arom, 6 CH arom), 124.14, 124.16, 124.21, 127.51, 129.55, 137.54,

ES 2 395 649 Al

144.95, 145.76, 146.85. Analytical data: Anal. Calcd for C43H52N2Pd C, 73.43; H, 7.45; N, 3.98. Experimental: C, 72.75; H, 7.52; N 3.97.

Spectroscopic data for (SIPr) Pd (styrene) 2: IR (nujol): v (C = C) = 1504 cm-1. 1H NMR (400 MHz, C6D6) 8 0.86

5 (d, J = 7.2 Hz, 24H, CH (CH3) 2), 2.78 (wide s, 2H, CH olefin), 2.85 (wide s, 2H, CH olefin), 3.13 (sept, J = 7.2 Hz , 4H, CH (CH3) 2), 3.26 (s, 4H, CH2 imid),), 3.53 (broad s, 2H, CH olefin), 6.29 (d, J = 7.2 Hz, 2H aromatic styrene). 13C NMR (100 MHz, C6D6) 8 22.10 (CH (CH3) 2), 52.42 (s, CH2 imid), 52.90 (s, CH2 olefin), 78.25 (s, CH olefin), 122.74, 122.95, 123.28, 127.44, 136.95, 145.95, 227.65 (Ccarbeno). Analytical data: Anal. Calcd for C43H52N2Pd C, 73.22; H, 7.72; N, 3.97. Experimental: C, 72.52; H, 7.81; N 3.93.

10 Example 2: Synthesis of complexes (NHC) Ni (styrene) 2

15 In the case of nickel complexes, bis (1,5-cyclooctadiene) nickel (0) (Ni (cod) 2) was used as the starting material.

Synthesis of complexes (NHC) Ni (styrene) 2 included the preparation of the following nickel complexes (0) with 2 coordinated styrene molecules and an N-heterocyclic carbine ligand [NHC = IPr (1,3-bis (2, 6-diisopropylphenyl) 20 imidazol-2-ylidene) or SIPr (1,3-bis (2,6-diisopropylphenyl) -4,5-dihydroimidazol-2-ylidene)]:

THF NHC

+ excess

NHC Ni

temp. amb. 10 min

Scheme 2: synthesis of complexes (NHC) Ni (styrene) 2

Preparation of the complexes (NHC) Ni (styrene) 2 (NHC = IPr and SIPr). The two complexes (NHC) Ni (styrene) 2 with NHC = IPr and NHC = SIPr were synthesized following a procedure similar to that described by Navarro and collaborators for the dmfu adduct (Berini, C .; Winkelmann, OH; Otten, J. ; Vicic, DA; Navarro, O. Chem. Eur. J. 2010, 16, 6857-6860).

A mixture of 1.0 g of 1,3-bis (2,6-diisopropylphenyl) imidazolium chloride (IPr · HCl) (2.35 mmol) and 290 mg potassium tert-butoxide (2.59 mmol) was stirred in THF (20 mL ) for an hour. The solution obtained contained 1,3-bis (2,6-diisopropylphenyl) imidazolidene, which was filtered and added onto a solution of 0.64 g of bis (1,5-cyclooctadiene) nickel (0) [Ni (cod) 2] (2.33 mmol ) and 2 mL of styrene (18.8 mmol) in 20 mL of THF, previously

35 stirred for 10 min. The resulting orange red solution was stirred for 2 h. It was filtered through celite and dried under reduced pressure. The solid obtained was redissolved in 5 mL of THF and petroleum ether was added, observing the precipitation of the complex (IPr) Ni (styrene) 2 as an orange crystalline solid (1.28 g,

2.1 mmol, 90%).

40 Spectroscopic data for (IPr) Ni (styrene) 2 were as follows: IR (nujol): v (C = C) = 1497 cm-1. 1H NMR (400 MHz, C6D6): 5 0.85 (wide s, 6 H, CH (CH3) 2), 1.10 (wide s, 6 H, CH (CH3) 2), 1.45 (wide s, 6 H, CH ( CH3) 2), 2.65 (broad d, 2 H, olefin CH), 2.73 (broad d, 2 H, olefin CH), 2.84 (wide s, CH (CH3) 2 2 H), 3.22 (m (br), CH olefin 2 H),

3.33 (wide s, CH (CH3) 2 2 H), 6.12 (s (br), 2 H). 6.5-7.2 (CH arom). 13C NMR (100 MHz, C6D6): 5 21.47 (CH (CH3) 2),

22.12 (CH (CH3) 2), 24.79 (CH (CH3) 2), 26.41 (CH (CH3) 2), 27.74 (CH (CH3) 2), 28.4 (CH (CH3) 2), 49.19 (CH2 olefin) , 72.26 45 (CH olefin), 126.7 (CH imid), 123.78, (4C arom, 6CH arom), 123.84, 125.19, 126.71, 129.15, 137.02, 145.32,

ES 2 395 649 Al

146.15, 146.17, 204.14 (Ccarbeno). Analytical data: Anal. Calcd for C47H60N2NiO (with crystallization THF) C, 77.58; H, 8.31; N, 3.85. Experimental: C, 77.98; H, 8.25; N 3.34.

Spectroscopic data for (SIPr) Ni (styrene) 2: IR (nujol): v (C = C) = 1493 cm-1. 1H NMR (400 MHz, C6D6): 5 0.68

5 (d, J 6.43 Hz, 6 H), 0.7 (d, J 7.03 Hz, 6 H), 0.80 (d, J 7.04 Hz, 6 H), 1.07 (d, J 7.01 Hz, 6 H), 1.912 ( s, 2H), 1,947 (s, 2H), 2.38 (d, J 9.38 Hz, 2 H), 2.47 (d, J 12.89 Hz, 2 H), 2.58 (m, 2 H), 2.96 (d, J 9.37 Hz, 2 H), 2.99 (d, J 9.36 Hz, 2 H), 3.08 (m, 2H) 6.12 (d, J 7.81 Hz, 2 H), 6.8-7.15 (CH arom). 13C NMR (100 MHz, C6D6): 5 23.10 (CH (CH3) 2), 23.27 (CH (CH3) 2), 26.49 (CH (CH3) 2), 26.84 (CH (CH3) 2), 28.24 (CH ( CH3) 2), 28.80 (CH (CH3) 2), 50.43 (CH imid), 53.91 (CH2 olefin), 72.86 (CH olefin), 123.33 (4C arom, 6CH arom), 124.27, 124.71, 124.98, 126.5, 128.94 , 138.33, 146.56,

10 146.87, 147.91, 204.52 (Ccarbeno). Analytical data: Anal. Calcd for C43 H54 N2Ni C, 78.54; H, 8.28; N, 4.26. Experimental: C, 78.45; H, 8.61; N 4.01.

ES 2 395 649 Al

Claims (6)

1. compound of general formula I 5 where M is a metal in oxidation state 0, selected from Pd or Ni NHC is an N-heterocyclic carbine ligand, 2. A compound of the general formula I according to claim 1 wherein the NHC N-heterocyclic carbine ligand is selected from 1,3-bis (2,6-diisopropylphenyl) imidazol-2-ylidene or 1,3-bis (2 , 6-diisopropylphenyl) -4,5-dihydroimidazol2-ylidene. 3. Method of synthesis of compounds of general formula I according to any of claims 1-2 where M is a metal in oxidation state 0, selected from Pd or Ni, NHC is an N-heterocyclic carbine ligand, characterized in that the compound of general formula I is synthesized from a metal-M complex together with an excess of styrene and a base, under an inert atmosphere of nitrogen, free of O2, and at room temperature. 4. Method of synthesis of compounds of general formula I according to claim 3, wherein M is Pd, the metal-M complex is NHC-Pd (allyl) Cl, the base is potassium tertbutoxide in isopropanol. Method of synthesis of compounds of general formula I according to claim 3, wherein M is Ni, the metal-M complex is bis (1,5-cyclooctadiene) nickel (0), in THF as the reaction medium and comprises the NHC addition. 6. Method of synthesis of compounds of general formula I according to any of claims 3-5, 30 where the N-heterocyclic carbine ligand NHC is selected from 1,3-bis (2,6-diisopropylphenyl) -imidazol-2-ylidene or 1,3-bis (2,6-diisopropylphenyl) -4,5-dihydroimidazole-2 -ilidene. 7. Use of the compound of general formula I according to any of claims 1-2, as catalyst. SPANISH OFFICE OF THE PATENTS AND BRAND Application number: 201131232 SPAIN Date of submission of the application: 07/19/2011 Priority Date: REPORT ON THE STATE OF THE TECHNIQUE 51 Int. Cl.: See Additional Sheet RELEVANT DOCUMENTS

Category

56 Documents cited Claims Affected

TO

KANTCHEV, E.A.B. et al. "Palladium Complexes of N-Heterocyclic Carbenes as Catalysts for Cross-Coupling Reactions-A Synthetic Chemist’s Perspective." Angewandte Chemie International Edition, 2007, Volume 46, pages 2768-2813. See page 2769, summary; page 2777, scheme 23; page 2779, figure; page 2781, scheme 44. 1-7

TO

BACCIU, D. et al. "Palladium-Mediated Oxidative Addition and Reductive Elimination Of Imidazolium Salts at C4 and C5". Angewandte Chemie International Edition, 2005, Volume 44, pages 5282-5284. [Published online on 07/22/2005]. See page 5283, scheme 2. 1-7

TO

WANG, C.-Y. "Palladium (II) complexes containing a bulky pyridinyl N-heterocyclic carbene ligand: Preparation and reactivity." Journal of Organometallic Chemistry, 2007, Volume 692, pages 3976-3983. [Available online on 06.15.2007]. See page 3976, summary; page 3978, scheme 2 and equation 2. 1-7

TO

MARION, M. et al. “Modified (NHC) Pd (allyl) Cl (NHC = N-Heterocyclic Carbene) Complexes for Room-Temperature Suzuki-Miyaura and Buchwald-Hartwig Reactions.” Journal of the American Chemical Society, 2006, Volume 128, pages 4101-4111. [Available online 03.04.2006]. See page 4101, summary; page 4103, figure 2. 1-7

TO

NAVARRO, O. et al. "General and efficient methodology for the Suzuki-Miyaura reaction in technical grade 2-propanol". Journal of Organometallic Chemistry, 2004, Volume 689, pages 3722-3727. [Available online on 07.05.2004]. See page 3723, figure 1, compounds 3-10. 1-7

TO

SELVAKUMAR, K. et al. "Synthesis of Monocarbenepalladium (0) Complexes and Their Catalytic Behavior in Cross-Coupling Reactions of Aryldiazonium Salts." Chemistry - A European Journal, 2002, Volume 8, Number 17, pages 3901-3906. See page 3902, compound 1. 1-7

Category of the documents cited X: of particular relevance Y: of particular relevance combined with other / s of the same category A: reflects the state of the art O: refers to unwritten disclosure P: published between the priority date and the date of priority submission of the application E: previous document, but published after the date of submission of the application

This report has been prepared • for all claims • for claims no:

Date of realization of the report 25.04.2012

Examiner G. Esteban García Page 1/4

REPORT OF THE STATE OF THE TECHNIQUE Application number: 201131232 CLASSIFICATION OBJECT OF THE APPLICATION C07F15 / 00 (2006.01) C07F15 / 04 (2006.01) B01J31 / 28 (2006.01) Minimum documentation sought (classification system followed by classification symbols) C07F, B01J Electronic databases consulted during the search (name of the database and, if possible, terms of search used) INVENES, EPODOC, WPI, REGISTRY, CAPLUS, EMBASE, XPESP, NPL, CHEMSPIDER State of the Art Report Page 2/4  WRITTEN OPINION Application number: 201131232 Date of Written Opinion: 25.04.2012 Statement

Novelty (Art. 6.1 LP 11/1986)

Claims Claims 1-7 IF NOT

Inventive activity (Art. 8.1 LP11 / 1986)

Claims Claims 1-7 IF NOT

The application is considered to comply with the industrial application requirement. This requirement was evaluated during the formal and technical examination phase of the application (Article 31.2 Law 11/1986).  Opinion Base.- This opinion has been made on the basis of the patent application as published. State of the Art Report Page 3/4  WRITTEN OPINION Application number: 201131232  1. Documents considered.- The documents belonging to the state of the art taken into consideration for the realization of this opinion are listed below.

Document

Publication or Identification Number publication date

D01

KANTCHEV, E.A.B. et al. Angewandte Chemie International Edition, 2007, Vol. 46, pp. 2768-2813 2007

D02

BACCIU, D. et al. Angewandte Chemie International Edition, 2005, Vol. 44, pp. 5282-5284 07/22/2005

D03

WANG, C.-Y. Journal of Organometallic Chemistry, 2007, Vol. 692, pp. 3976-3983 06.15.2007

D04

MARION, M. et al. Journal of the American Chemical Society, 2006, Vol. 128, pp. 4101-4111 04.04.2006

 2. Statement motivated according to articles 29.6 and 29.7 of the Regulations for the execution of Law 11/1986, of March 20, on Patents on novelty and inventive activity; quotes and explanations in support of this statement The object of the invention is a compound of general formula (I) comprising a metal (Pd or Ni), two styrene groups and an N-heterocyclic carbine ligand; a process for the synthesis of said compound (I); and its use as a catalyst. Document D01 discloses a review of palladium complexes comprising N-heterocyclic carbons and their use as catalysts in cross-coupling reactions (see page 2769, summary). Among the disclosed palladium complexes is compound 78 (see page 2777, scheme 23), which comprises 1,3-bis (2,4,6-trimethylphenyl) -4,5dihydroimidazol-2-ylidene as N-heterocyclic carbine and an allyl ligand; compound 106, which comprises 1,3-bis (2,6-diisopropylphenyl) -imidazol-2-ylidene as carben and a divinyl silicon derivative ligand (see page 2779, figure); and complexes 154 and 155, which also comprise a carbine and an alkenyl ligand (allylbenzene or methylalkyl) (see (page 2781, scheme 44). All these complexes differ from the complex of the invention in the structure of the alkenyl ligand (which in the compound of the invention is styrene) and / or in the number of ligands present (which in the compound of the invention is 2). Document D02 discloses the platinum complex 5b, which comprises an N-heroinic carbine, such as 1,3-bis (2,4,6-trimethylphenyl) -imidazol-2-ylidene and two styrene ligands (see page 5283, scheme 2) , and which differs from the compound of the invention in the nature of the present metal atom, which is palladium or nickel. Document D03 discloses a series of palladium complexes comprising an imidazole-derived N-heterocyclic carbine and an allyl group (see page 3978, scheme 2, compounds I-III; equation 2, compound IV), and which can be used as catalysts in reactions of Suzuki-Miyaura and Mizoroki-Heck (see page 3976, summary). Document D04 discloses a series of palladium complexes with application as catalysts in reactions of Suzuki-Miyuaura and Buchwald-Hartwig (see page 4101, summary), among which are compounds 5-7, which possess a carbine group derived from imidazole or dihydroimidazole, a chlorine atom and a ligand containing an allyl moiety, such as allyl, methylalkyl, 3,3-dimethylalkyl or cinnamonyl (see page 4103, Figure 2). The complexes disclosed in documents D03 and D04 differ from the complex of the invention in the structure of the alkenyl ligand (which in the compound of the invention is styrene) and / or in the number of alkenyl ligands present. The cited documents show only the state of the art of the field to which the invention belongs. None of them, taken alone or in combination with the others, contain any disclosure or suggestion that could lead the person skilled in the art to a complex of general formula (I) comprising Pd or Ni as metal, two styrene groups and a carbine ligand N-heterocyclic (independent claim 1); and therefore, also towards a process for the synthesis of said compound (I) (independent claim 3); nor towards its use as a catalyst (independent claim 7). Consequently, it is considered that the object of claims 1-7 meets the requirements of novelty and inventive activity set forth in Articles 6.1 and 8.1 of the Patent Law. State of the Art Report Page 4/4