Synthesis,structure, and activity of (PhCH2NH2)2CuCl2 for oxidative coupling of 2‐naphthylamine

(PhCH₂NH₂)₂CuCl₂ ( 2 ), an effective oxidation reagent for oxidative coupling of 2‐naphthylamine ( 1 ) to form 2,2′‐diamino‐1,1′‐binaphthyl ( 4 ), is studied. Oxidative coupling of 2‐naphthylamine ( 1 ) is carried out at room temperature in methanol by (PhCH₂NH₂)₂CuCl₂ ( 2 ), which is prepared from CuCl₂·2H₂O and benzylamine in methanol, to give a novel copper complex, [{1,1′‐(C₁₀H₆)₂‐2,2′‐(NH₂)₂}₂CuCl]Cl·CH₃OH·3H₂O ( 3 ), in good yield. Treatment of 3 with aqueous HCl (37%), followed by addition of NH₃·H₂O (25%), gives 2,2′‐diamino‐1,1′‐binaphthyl ( 4 ) in a moderate yield (total yield from 1 : > 70%). Both 2 and 3 have been characterized by various techniques, such as infrared spectroscopy, elemental analyses and X‐ray diffraction. Copyright © 2007 John Wiley & Sons, Ltd.     

Synthesis,characterization and catalytic activity of new aminomethyldiphosphine–Pd(II) complexes for Suzuki cross‐coupling reaction

A new range of CF₃‐substituted aminomethyldiphosphine (P―C―N) ligands ((C₆H₅)₂PCH₂)₂NR (R = ―C₆H₄(2‐CF₃) ( 1 ), ―C₆H₄(3‐CF₃) ( 1b ) has been synthesized from 2‐(trifluoromethyl)aniline and 3‐(trifluoromethyl)aniline with diphenylphosphine. The aminomethyldiphosphine ligands were reacted with Pd(cod)Cl₂ to give corresponding metal complexes, PdLCl₂ ( 2a , 2b ). The aminomethyldiphosphine–palladium compounds were characterized by utilizing several methods including NMR (¹H, ¹³C, ³¹P) and elemental analysis. These compounds were used as catalysts in Suzuki cross‐coupling reaction of aryl chlorides and bromides. The effect of base was also investigated in this current project. CF₃‐substituted aminomethyldiphosphine–palladium complexes were found to be efficient catalysts in Suzuki cross‐coupling reaction of activated and deactivated aryl boronic acids. Copyright © 2013 John Wiley & Sons, Ltd.     

Application of ortho‐palladated homoveratrylamine complex containing mixed phosphorus–nitrogen donors in the Suzuki reaction

The catalytic activity of [Pd{C₆H₂(CH₂CH₂NH₂)‐(OMe)₂,3,4}Br(PPh₃)] monomeric ortho‐palladated complex of homoveratrylamine and triphenylphosphine was investigated in the Suzuki cross‐coupling reaction of various aryl halides with aryl boronic acids. The substituted biaryls were produced in excellent yields using a catalytic amount of this complex in ethanol at 60°C. Copyright © 2012 John Wiley & Sons, Ltd.     

Unexpected Reaction Course of 3‐Amino‐5‐aryl‐1H‐pyrazoles with Dialkyl Dicyanofumarates

On treatment of 3‐amino‐5‐aryl‐1H‐pyrazoles 1 with dialkyl dicyanofumarates (=(E)‐but‐2‐enedioates) 4 in boiling 1,2‐dichloroethane, two competitive reactions occurred leading to 3‐aryl‐5‐cyano‐6,7‐dihydro‐6‐oxo‐1H‐pyrazolo[3,4‐b]pyridine‐4‐carboxylates 10 and 7‐amino‐2‐arylpyrazolo[1,5‐a]pyrimidine‐5,6‐dicarboxylates 11 . In DMF at room temperature, as well as at 100°, only compounds 10 were isolated. The formation of the major products of type 10 was rationalized via Michael addition of 1 as a C(4)‐nucleophile onto 4 , followed by HCN elimination and lactamization. On the other hand, the minor products 11 result from a Michael addition of 1 onto 4 via the NH₂ group, and subsequent HCN elimination and cyclization. The structures of the products have been established by X‐ray crystallography.     

Highly efficient orthopalladated complexes of second and third benzyl amine for catalyzing the Suzuki cross‐coupling reaction

In this work, ortho‐palladated complexes [Pd(µ‐Cl)(C₆H₄CH₂ NRR′‐κ²‐C,N)]₂ and [Pd(C₆H₄CH₂NH₂‐2‐C,N)Cl(Y)] were tested in the Suzuki–Miyaura cross‐coupling reaction. Cyclopalladated Pd(II) complexes as thermally stable catalysts can activate aryl bromides and chlorides. These complexes were active and efficient catalysts for the Suzuki–Miyaura reaction of aryl bromides and even less reactive aryl chlorides. The cross‐coupled products of a variety of aryl bromides and aryl chloride with phenylboronic acid in methanol as solvent at 60 °C were produced in excellent yields. Copyright © 2010 John Wiley & Sons, Ltd.     

Synthesis of substituted biaryls via Suzuki,Stille and Hiyama cross‐coupling and homo‐coupling reactions by CN‐dimeric and monomeric ortho‐palladated catalysts

The catalytic activity of dimeric [Pd{C₆H₂(CH₂CH₂NH₂)–(OMe)₂,2,3}(μ‐Br)]₂ and monomeric [Pd{C₆H₂(CH₂CH₂NH₂)–(OMe)₂,2,3}Br(PPh₃)] complexes as efficient, stable and air‐ and moisture‐tolerant catalysts was investigated in the Suzuki, Stille and Hiyama cross‐coupling and homo‐coupling reactions of various aryl halides. Substituted biaryls were produced in excellent yields in short reaction times using catalytic amounts of these complexes. The monomeric complex was demonstrated to be more active than the corresponding dimeric catalyst for the cross‐coupling reaction of unreactive aryl bromides and chlorides. The combination of homogeneous metal catalysts and microwave irradiation gave higher yields of products in shorter reaction times. Copyright © 2013 John Wiley & Sons, Ltd.     

The Nitrogen‐Assisted Triphenylphosphine Displacement of 3‐Hydroxypyridine and 3‐Aminopyridine Ligands in Palladium(II) Complexes: Crystal Structures of [Pd(PPh3)Br]2{μ,η2‐C5H3N(OH)}2 and [Pd(PPh3)Br]2{μ,η2‐C5H3N(NH2)}2

Treatment of Pd(PPh₃₎₄ with 2‐bromo‐3‐hydroxypyridine [C₅H₃N(OH)Br] and 3‐amino‐2‐bromopyridine [C₅H₃N(NH₂)Br] in dichloromethane at ambient temperature cause the oxidative addition reaction to produce the palladium complex [Pd(PPh₃₎₂{η¹‐C₅H₃N(OH)}(Br)], 2 and [Pd(PPh₃₎₂{η¹‐C₅H₃N(NH₂)}(Br)], 3 , by substituting two triphenylphosphine ligands, respectively. In dichloromethane solution of complexes 2 and 3 at ambient temperature for 3 days, it undergo displacement of the triphenylphosphine ligand to form the dipalladium complexes [Pd(PPh₃)Br]₂{μ,η²‐C₅H₃N(OH)}₂, 4 and [Pd(PPh₃)Br]₂{μ,η²‐C₅H₃N(NH₂)}₂, 5 , in which the two 3‐hydroxypyridine and 3‐aminopyridine ligands coordinated through carbon to one metal center and bridging the other metal through nitrogen atom, respectively. Complexes 4 and 5 are characterized by X‐ray diffraction analyses.     

Co‐catalyst effects on the thermal stability/activity of N,N,N‐Co ethylene polymerization Catalysts Bearing Fluoro‐Substituted N‐2,6‐dibenzhydrylphenyl groups

The unsymmetrical bis (arylimino)pyridines, 2‐[CMeN{2,6‐{(4‐FC₆H₄)₂CH}₂–4‐t‐BuC₆H₂}]‐6‐(CMeNAr)C₅H₃N (Ar = 2,6‐Me₂C₆H₃ L1 , 2,6‐Et₂C₆H₃ L2 , 2,6‐i‐Pr₂C₆H₃ L3 , 2,4,6‐Me₃C₆H₂ L4 , 2,6‐Et₂–4‐MeC₆H₂ L5 ), each containing one N‐aryl group bedecked with ortho‐substituted fluorobenzhydryl groups, have been employed in the preparation of the corresponding five‐coordinate cobalt (II) chelates, LCoCl₂ ( Co1 – Co5 ); the symmetrical comparator [2,6‐{CMeN(2,6‐(4‐FC₆H₄)₂CH)₂–4‐t‐BuC₆H₂}₂C₅H₃N]CoCl₂ (Co6) is also reported. All cobaltous complexes are paramagnetic and have been characterized by ¹H/¹⁹F NMR spectroscopy, FT‐IR spectroscopy and elemental analysis. The molecular structures of Co3 and Co6 highlight the different degrees of steric protection given to the metal center by the particular N‐aryl group combination. Depending on the aluminoxane co‐catalyst employed to activate the cobalt precatalyst, distinct variations in thermal stability and activity of the catalyst towards ethylene polymerization were exhibited. In particular with MAO, the resultant catalysts reached their optimal performance at 70 °C delivering high activities of up to 10.1 × 10⁶ g PE (mol of Co)^?1 h^?1 with Co1  >  Co4  >  Co2  >  Co5  >  Co3 >>  Co6 . On the other hand, using MMAO, the catalysts operate most effectively at 30 °C but are by comparison less productive. In general, the polyethylenes were highly linear, narrowly disperse and displayed a wide range of molecular weights [M_w range: 18.5–58.7 kg mol^?1 (MAO); 206.1–352.5 kg mol^?1 (MMAO)].     

Reaction of (η5‐C5H5)Fe(CO)2I with Anionic Bidentate Phosphine Ligands PPh2(o‐C6H4NHLi) or PPh2(o‐C6H4OLi)

The o‐substituted hybrid phenylphosphines, PPh₂(o‐C₆H₄NH₂) and PPh₂(o‐C₆H₄OH), could be deprotonated with LDA or n‐BuLi to yield PPh₂(o‐C₆H₄NHLi) and PPh₂(o‐C₆H₄OLi), respectively. When added to a solution of (η⁵‐C₅H₅)Fe(CO)₂I at room temperature, these two lithiated reagents produce a chelated neutral complex 1 (η⁵‐C₅H₅)Fe(CO)[C(O)NH(o‐C₆H₄)PPh₂‐C,P‐η²] for the former and mainly a zwitterionic complex 2 , (η⁵‐C₅H₅)Fe⁺(CO)₂[PPh₂(o‐C₆H₄O^?)] for the latter. Complex 1 could easily be protonated and then decarbonylated to give 4 [(η⁵‐C₅H₅)Fe(CO){NH₂(o‐C₆H₄)PPh₂‐N,P‐η²}⁺]. Complexes 1 and 4‐I have been crystallographically characterized with X‐ray diffraction.     

Accelerated Heck reaction using ortho‐palladated complex with controlled microwave heating

Palladium‐catalyzed Heck couplings utilizing [Pd{C₆H₂(CH₂CH₂NH₂)‐(OMe)₂,3,4} (µ‐Br)]₂ palladacycle catalyst and microwave irradiation lead to formation of different coupling products. This complex is an active and efficient catalyst for the Heck reaction of aryl iodides, bromides and even less reactive chlorides. The cross‐coupled products were produced in excellent yields. The reaction time was reduced from hours to minutes and full conversion was achieved under microwave irradiation. Copyright © 2009 John Wiley & Sons, Ltd.     

Synthesis and Characterization of m‐Terphenyl (1,3‐Diphenylbenzene) Compounds Containing Trifluoromethyl Groups

The bis(silyl)triazene compound 2,6‐(Me₃Si)₂‐4‐Me‐1‐(N?N? NC₄H₈)C₆H₂ ( 4 ) was synthesized by double lithiation/silylation of 2,6‐Br₂‐4‐Me‐1‐(N?N? NC₄H₈)C₆H₂ ( 1 ). Furthermore, 2,6‐bis[3,5‐(CF₃)₂‐C₆H₃]‐4‐Me‐C₆H₂‐1‐(N?N? NC₄H₈)C₆H₂ derivative 6 can be easily synthesized by a C,C‐bond formation reaction of 1 with the corresponding aryl‐Grignard reagent, i.e., 3,5‐bis[(trifluoromethyl)phenyl]magnesium bromide. Reactions of compound 4 with KI and 6 with I₂ afforded in good yields novel phenyl derivatives, 2,6‐(Me₃Si)₂‐4‐MeC₆H₂? I and 2,6‐bis[3,5‐(CF₃)₂? C₆H₃]‐4‐MeC₆H₂? I ( 5 and 7 , resp.). On the other hand, the analogous m‐terphenyl 1,3‐diphenylbenzene compound 2,6‐bis[3,5‐(CF₃)₂? C₆H₃]C₆H₃? I ( 8 ) could be obtained in moderate yield from the reaction of (2,6‐dichlorophenyl)lithium and 2 equiv. of aryl‐Grignard reagent, followed by the reaction with I₂. Different attempts to introduce the ^tBu (Me₃C) or neophyl (PhC(Me)₂CH₂) substituents in the central ring were unsuccessful. All the compounds were fully characterized by elemental analysis, melting point, IR and NMR spectroscopy. The structure of compound 6 was corroborated by single‐crystal X‐ray diffraction measurements.     

Addition of Hydrogen or Ammonia to a Low‐Valent Group 13 Metal Species at 25 °C and 1 Atmosphere

Mild‐mannered : The low‐valent aryl gallium(I) species :GaAr′ (Ar′=2,6‐(2,6‐iPr₂C₆H₃)₂C₆H₃) undergoes addition to H₂ or NH₃ at room temperature and one atmosphere of pressure to afford 1 or 2 (see scheme), which were characterized by X‐ray crystallography and NMR and IR spectroscopy.

     

Rare‐Earth‐Metal–Hydrocarbyl Complexes Bearing Linked Cyclopentadienyl or Fluorenyl Ligands: Synthesis,Catalyzed Styrene Polymerization,and Structure–Reactivity Relationship

A series of rare‐earth‐metal–hydrocarbyl complexes bearing N‐type functionalized cyclopentadienyl (Cp) and fluorenyl (Flu) ligands were facilely synthesized. Treatment of [Y(CH₂SiMe₃)₃(thf)₂] with equimolar amount of the electron‐donating aminophenyl‐Cp ligand C₅Me₄H‐C₆H₄‐o‐NMe₂ afforded the corresponding binuclear monoalkyl complex [({C₅Me₄‐C₆H₄‐o‐NMe(μ‐CH₂)}Y{CH₂SiMe₃})₂] ( 1 a ) via alkyl abstraction and C? H activation of the NMe₂ group. The lutetium bis(allyl) complex [(C₅Me₄‐C₆H₄‐o‐NMe₂)Lu(η³‐C₃H₅)₂] ( 2 b ), which contained an electron‐donating aminophenyl‐Cp ligand, was isolated from the sequential metathesis reactions of LuCl₃ with (C₅Me₄‐C₆H₄‐o‐NMe₂)Li (1 equiv) and C₃H₅MgCl (2 equiv). Following a similar procedure, the yttrium‐ and scandium–bis(allyl) complexes, [(C₅Me₄‐C₅H₄N)Ln(η³‐C₃H₅)₂] (Ln=Y ( 3 a ), Sc ( 3 b )), which also contained electron‐withdrawing pyridyl‐Cp ligands, were also obtained selectively. Deprotonation of the bulky pyridyl‐Flu ligand (C₁₃H₉‐C₅H₄N) by [Ln(CH₂SiMe₃)₃(thf)₂] generated the rare‐earth‐metal–dialkyl complexes, [(η³‐C₁₃H₈‐C₅H₄N)Ln(CH₂SiMe₃)₂(thf)] (Ln=Y ( 4 a ), Sc ( 4 b ), Lu ( 4 c )), in which an unusual asymmetric η³‐allyl bonding mode of Flu moiety was observed. Switching to the bidentate yttrium–trisalkyl complex [Y(CH₂C₆H₄‐o‐NMe₂)₃], the same reaction conditions afforded the corresponding yttrium bis(aminobenzyl) complex [(η³‐C₁₃H₈‐C₅H₄N)Y(CH₂C₆H₄‐o‐NMe₂)₂] ( 5 ). Complexes 1 – 5 were fully characterized by ¹H and ¹³C NMR and X‐ray spectroscopy, and by elemental analysis. In the presence of both [Ph₃C][B(C₆F₅)₄] and AliBu₃, the electron‐donating aminophenyl‐Cp‐based complexes 1 and 2 did not show any activity towards styrene polymerization. In striking contrast, upon activation with [Ph₃C][B(C₆F₅)₄] only, the electron‐withdrawing pyridyl‐Cp‐based complexes 3 , in particular scandium complex 3 b , exhibited outstanding activitiy to give perfectly syndiotactic (rrrr >99 %) polystyrene, whereas their bulky pyridyl‐Flu analogues ( 4 and 5 ) in combination with [Ph₃C][B(C₆F₅)₄] and AliBu₃ displayed much‐lower activity to afford syndiotactic‐enriched polystyrene.     

Effect of core substituents on the intramolecular exchange interaction in N,N′‐dioxy‐2,6‐diazaadamantane biradical: DFT studies

Density‐functional theory calculations of a series of organic biradicals on the basis of the N,N′‐dioxy‐2,6‐diazaadamantane core with different substituents at carbon atoms adjacent to the nitroxyl groups have been performed by the UB3LYP/6‐311++G(2d,2p) method. Using the breaking symmetry approach, the values of the exchange interaction parameter, J, between the radical centers are calculated. It is shown that the intramolecular exchange interaction for the most part is ferromagnetic in nature, but the J parameter gradually decreases, changing its sign to antiferromagnetic interaction for the last substituent in the following sequence: CF₃(CH₃)COH > CH₂F(H)COH > CH₂OH > H > CBr₃ > CH₂F > CCl₃ > CF₃ > CH₂Br > CH₂Cl > CH₃ > C₂H₅ > C₃H₇ > i‐C₄H₉ > F > Br > OCH₃ > Cl > CH₂C₆H₅. The calculations at the UHSEH1PBE/6‐311++G(2d,2p) level with the most of substituents show nearly the same variation sequence for the J parameter. It is concluded that spin polarization effects in the diazaadamantane cage and a direct through‐space antiferromagnetic exchange interaction between the nitroxyl groups are the main mechanisms contributing to the exchange interaction parameter value in the studied series of compounds. The exchange coupling constant, J, depends on the electronic effects and geometry of the substituents, as well as on their specific interactions with the nitroxyl radical groups.     

The Nitrogen‐Assisted Triphenylphosphine Displacement of Methylpyridine Ligand in Palladium(II) Complex: Crystal Structures of [Pd(PPh3)2{η1‐C5H3N(CH3)}(Br)] and [Pd(PPh3)Br]2{μ,η2‐C5H3N(CH3)}2

Treatment of Pd(PPh₃)₄ with 2‐bromo‐4‐methylpyridine, C₅H₃N(CH₃)Br, in dichloromethane at ?20 °C causes the oxidative addition reaction to produce the palladium complex [Pd(PPh₃)₂ {η¹‐C₅H₃N(CH₃)}(Br)], 2 , by substituting two triphenylphosphine ligands. In a dichloromethane solution of complex 2 at room temperature for 3 h, it undergoes displacement of the triphenylphosphine ligand to form the dipalladium complex [Pd(PPh₃)Br]₂{μ,η²‐C₅H₃N(CH₃)}₂, 3 , in which the two 4‐methylpyridine ligands coordinated through carbon to one metal center and bridging the other metal through the nitrogen atom. Complexes 2 and 3 are characterized by X‐ray diffraction analyses.     

Regioselective ortho‐Metallation of 2‐Diphenylphosphanylpyridine and (2‐(2‐Diphenylphosphanyl)phenyl)‐1‐3‐dioxalane with Methyltetrakis(trimethylphosphane)cobalt(I)

Co(CH₃)(PMe₃)₄ forms 100 % regioselectively with (2‐(2‐diphenylphosphanyl)phenyl)‐1,3‐dioxalane and 2‐diphenylphosphanyl‐pyridine, by elimination of methane, the four‐membered metallacycles Co{(C₃O₂HC₆H₃)P(C₆H₅)₂}(PMe₃)₃ ( 1 ) and Co{(CNC₄H₃)P(C₆H₅)₂}(PMe₃)₃ ( 4 ). The regioselectivity is independent of the steric requirement of the ortho substituent in the 2‐diphenylphosphanylaryl‐ligands. Oxidative addition with iodomethane transforms 1 and 4 into octahedral, diamagnetic low‐spin d⁶ complexes Co(CH₃)I‐{(C₃O₂HC₆H₃)P(C₆H₅)₂}(PMe₃)₂ ( 2 ) and Co(CH₃)I‐{(CNC₄H₃)P(C₆H₅)₂}(PMe₃)₂ ( 5 ). Under an atmosphere of carbon monoxide, insertion into the Co‐C bond results in ring expansion by forming the new assembled phosphanylbenzoyl complexes Co{(C₄O₃HC₆H₃)‐P(C₆H₅)₂}CO(PMe₃)₂ ( 3 ) and Co{(OCNC₄H₃)P(C₆H₅)₂}CO(PMe₃)₂ ( 6 ). The three different types of cobaltacycles are supported by X‐ray diffraction of 1 , 3 , 5 and 6 .     

Accelerated Heck reaction using ortho‐palladated complex in a nonaqueous ionic liquid with controlled microwave heating

The activity of {Pd[C₆H₂(CH₂CH₂NH₂)‐(OMe)₂,3,4] (µ‐Br)}₂ complex was investigated in the Heck–Mizoroki C C cross‐coupling reaction under conventional heating and microwave irradiation conditions in molten salt tetrabutylammonium bromide as the solvent and promoter at 130 °C. This complex in these conditions is an active and efficient catalyst for the Heck reaction of aryl iodides, bromides and even chlorides, and also arenesulfonyl chlorides. Copyright © 2011 John Wiley & Sons, Ltd.     

Metall‐π‐Aren‐Wechselwirkungen in den Kristallstrukturen von zwei Lewis‐Donor‐freien Arylbis(cyclopentadienyl)lanthanoiden

Metal‐π‐Arene‐Interactions in the Solid‐State Structures of Two Lewis Donor‐Free Arylbis(cyclopentadienyl)lanthanoids Ar*Yb(C₅H₄Me)₂ ( 1 ) and Ar*SmCp₂ ( 2 ) (Ar* = 2,6‐Mes₂C₆H₃) have been obtained by the reaction of LiAr* with Yb(C₅H₄Me)₃ or SmCp₃ in toluene. Red crystals of 1 and orange crystals of 2 were characterized by X‐ray structure analysis. The lanthanoids are η⁵‐coordinated to the cyclopentadienyl ligands and η¹‐coordinated to the ipso carbon atom of the aryl groups. Additional π‐arene contacts to one mesityl group give rise to a different pyramidalisation of the metal centers, which depends on the size of the central lanthanoid atom.     

Preparation of linear α‐olefins to high‐molecular weight polyethylenes using cationic α‐diimine nickel(II) complexes containing chloro‐substituted ligands

A series of α‐diimine nickel(II) complexes containing chloro‐substituted ligands, [(Ar)N?C(C₁₀H₆)C?N(Ar)]NiBr₂ ( 4a , Ar = 2,3‐C₆H₃Cl₂; 4b , Ar = 2,4‐C₆H₃Cl₂; 4c , Ar = 2,5‐C₆H₃Cl₂; 4d , Ar = 2,6‐C₆H₃Cl₂; 4e , Ar = 2,4,6‐C₆H₂Cl₃) and [(Ar)N?C(C₁₀H₆)C?N(Ar)]₂NiBr₂ ( 5a , Ar = 2,3‐C₆H₃Cl₂; 5b , Ar = 2,4‐C₆H₃Cl₂; 5c , Ar = 2,5‐C₆H₃Cl₂), have been synthesized and investigated as precatalysts for ethylene polymerization. In the presence of modified methylaluminoxane (MMAO) as a cocatalyst, these complexes are highly effective catalysts for the oligomerization or polymerization of ethylene under mild conditions. The catalyst activity and the properties of the products were strongly affected by the aryl‐substituents of the ligands used. Depending on the catalyst structure, it is possible to obtain the products ranging from linear α‐olefins to high‐molecular weight polyethylenes. © 2006 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 44: 1964–1974, 2006     

Cross‐coupling reactions in water using ionic liquid‐based palladium(II)–phosphinite complexes as outstanding catalysts

Two new phosphinite ligands based on ionic liquids [(Ph₂PO)C₇H₁₄N₂Cl]Cl ( 1 ) and [(Cy₂PO)C₇H₁₄N₂Cl]Cl ( 2 ) were synthesized by reaction of 1‐(3‐chloro‐2‐hydoxypropyl)‐3‐methylimidazolium chloride, [C₇H₁₅N₂OCl]Cl, with one equivalent of chlorodiphenylphosphine or chlorodicyclohexylphosphine, respectively, in anhydrous CH₂Cl₂ and under argon atmosphere. The reactions of 1 and 2 with MCl₂(cod) (M = Pd, Pt; cod = 1,5‐cyclooctadiene) yield complexes cis‐[M([(Ph₂PO)C₇H₁₄N₂Cl]Cl)₂Cl₂] and cis‐[M(Cy₂PO)C₇H₁₄N₂Cl]Cl)₂Cl₂], respectively. All complexes were isolated as analytically pure substances and characterized using multi‐nuclear NMR and infrared spectroscopies and elemental analysis. The catalytic activity of palladium complexes based on ionic liquid phosphinite ligands 1 and 2 was investigated in Suzuki cross‐coupling. They show outstanding catalytic activity in coupling of a series of aryl bromides or aryl iodides with phenylboronic acid under the optimized reaction conditions in water. The complexes provide turnover frequencies of 57 600 and 232 800 h^?1 in Suzuki coupling reactions of phenylboronic acid with p‐bromoacetophenone or p‐iodoacetophenone, respectively, which are the highest values ever reported among similar complexes for Suzuki coupling reactions in water as sole solvent in homogeneous catalysis. Furthermore, the palladium complexes were also found to be highly active catalysts in the Heck reaction affording trans‐stilbenes. Copyright © 2014 John Wiley & Sons, Ltd.