Complexes 2e Research Articles

Iridium PCsp3P-type Complexes with a Hemilabile Anisole Tether

A series of iridium PCsp3P complexes based on bis(2-diisopropylphosphinophenyl)-2-anisoylmethane (PCanisHP) is reported. (PCanisP)Ir(H)Cl was generated from the C–H activation of the backbone by [Ir(COD)Cl]2 (COD = 1,5-cyclooctadiene), while the dihydride (PCanisP)Ir(H)2 was generated by hydride metathesis from (PCanisP)Ir(H)Cl. Both complexes are 18e octahedral complexes and water stable. The hemilability of the anisole tether was probed using CO and PMe3; multiple isomers, in which the anisole substituent was displaced, were generated, showing the flexibility of the ligand backbone. (PCanisP)Ir(H)2 showed deuterium incorporation in the hydride, backbone, and anisole positions upon moderate heating in C6D6. Both (PCanisP)Ir(H)Cl and (PCanisP)Ir(H)2 were precatalysts for transfer dehydrogenation of cyclooctane under moderate conditions.

Role of anagostic interactions in cycloplatination of telluroethers: Synthesis and structural characterization

Reactions of K2PtCl4 with TeRRʹ gave complexes of composition [PtCl2(TeRRʹ)2] (R/Rʹ = Ph2(1a), o-tol2 (1b), Mes2(1c), Ph/Mes (1d), o-tol/Mes (1e)). The complex [PtCl2(TeMes2)2] in refluxing THF afforded a mononuclear cyclometalated complex [PtCl{(CH2C6H2Me2-4,6)TeMes}(TeMes2)] (2). It tends to remain in equilibrium with a binuclear derivative [Pt(μ-Cl){(CH2C6H2Me2-4,6)TeMes}]2 (3) in CDCl3 solution. The complexes 1d and 1e did not undergo cyclometalation reaction under similar reaction conditions. The 2 on treatment with PPh3 gave [PtCl{(CH2C6H2Me2-4,6)TeMes}(PPh3)] (4). All the complexes have been characterized by elemental analysis and NMR (1H, 31P, 125Te, 195Pt) spectroscopy. Anagostic interactions have been recognised for facilitation of cyclometalation reactions. The molecular structures of trans-[PtCl2(TeMes2)2] (1c), trans-[PtCl2(PhTeMes)2] (1d), trans-[PtCl2(o-tolTeMes)2] (1e), [PtCl{(CH2C6H2Me2-4,6)TeMes}(TeMes2)] (2) and [PtCl{(CH2C6H2Me2-4,6)TeMes}(PPh3)] (4) have been established unambiguously by single crystal X-ray diffraction analyses.

Cobalt and nickel complexes supported by 2,6-bis(imidate)pyridyl ligands: Synthesis, characterization, and 1,3-butadiene polymerization studies

A series of 2,6-bis(imidate)pyridine ligated Co(II) and Ni(II) complexes with general formula of [2,6-(2,6-iPr2C6H3N=COR)2C5H3N]MX2 (R=Me, M=Co, X=Cl (1a); R=Me, M=Ni, X=Br (2a); R=Et, M=Co, X=Cl (1b); R=Et, M=Ni, X=Br (2b); R=iPr, M=Co, X=Cl (1c); R=iPr, M=Ni, X=Br (2c); R=CH2CF3, M=Co, X=Cl (1d); R=CH2CF3, M=Ni, X=Br (2d); R=Ph, M=Co, X=Cl (1e); R=Ph, M=Ni, X=Br (2e); R=CH2Ph, M=Co, X=Cl (1f); R=CH2Ph, M=Ni, X=Br (2f)) were synthesized. Determined by single crystal X-ray analysis, complexes 1e and 2c with NNN tridentate ligands adopted approximate distorted square pyramidal configurations whereas complex 1f with tridentate NNO ligand displayed a distorted square pyramidal configuration. Activated by methylaluminoxane (MAO), these complexes exhibited high cis-1,4 selectivity towards 1,3-butadiene polymerization. The structure of substituent and polymerization conditions significantly influenced the catalytic behaviors of the complexes. The addition of PPh3 to the Co(II)-based systems enhanced the catalytic activity and switched the selectivity from cis-1,4 to 1,2 manner.

Dichlorido(3-chloropyridine-N)[1,3-dialkylbenzimidazol-2-ylidene]palladium(II) complexes: Synthesis, characterization and catalytic activity in the arylation reaction

Six novel Pyridine Enhanced Precatalyst Preparation, Stabilization and Initiation (PEPPSI) themed palladium N-heterocyclic carbene (Pd-NHC) complexes (2a–f) were synthesized in good yields from the reaction of 1,3-dialkylbenzimidazolium salts with PdCl2 in the presence of K2CO3 as base in 3-chloropyridine. These synthesized complexes were characterized by means of elemental analysis, FT-IR, 1H and 13C NMR spectroscopic methods. The fully characterized novel complexes (2a–f) were tested as catalysts in the direct arylation of 2-n-propylthiazole, 2-n-butylthiophene and 2-n-butylfuran with different aryl bromides at 130°C for 1h. The complexes exhibited fairly high catalytic activities under the given conditions. The highest conversions were achieved when complexes 2a, 2e and 2f were used as catalysts in direct arylation.

Tris(pyrazolyl)methanides of the alkaline earth metals: influence of the substitution pattern on stability and degradation.

Trispyrazolylmethanides commonly act as strong tridentate bases toward metal ions. This expected coordination behavior has been observed for tris(3,4,5-trimethylpyrazolyl)methane (1a), which yields the alkaline-earth-metal bis[tris(3,4,5-trimethylpyrazolyl)methanides] of magnesium (1b), calcium (1c), strontium (1d), and barium (1e) via deprotonation of 1a with dibutylmagnesium and [Ae{N(SiMe3)2}2] (Ae = Mg, Ca, Sr, and Ba, respectively). Barium complex 1e degrades during recrystallization that was attempted from aromatic hydrocarbons and ethers. In these scorpionate complexes, the metal ions are embedded in distorted octahedral coordination spheres. Contrarily, tris(3-thienylpyrazolyl)methane (2a) exhibits a strikingly different reactivity. Dibutylmagnesium is unable to deprotonate 2a, whereas [Ae{N(SiMe3)2}2] (Ae = Ca, Sr, and Ba) smoothly metalates 2a. However, the primary alkaline-earth-metal bis[tris(3-thienylpyrazolyl)methanides] of Ca (2c), Sr (2d), and Ba (2e) represent intermediates and degrade under the formation of the alkaline-earth-metal bis(3-thienylpyrazolates) of calcium (3c), strontium (3d), and barium (3e) and the elimination of tetrakis(3-thienylpyrazolyl)ethene (4). To isolate crystalline compounds, 3-thienylpyrazole has been metalated, and the corresponding derivatives [(HPz(Tp))4Mg(Pz(Tp))2] (3b), dinuclear [(tmeda)Ca(Pz(Tp))2]2 (3c), mononuclear [(pmdeta)Sr(Pz(Tp))2] (3d), and [(hmteta)Ba(Pz(Tp))2] (3e) have been structurally characterized. Regardless of the applied stoichiometry, magnesiation of thienylpyrazole 3a with dibutylmagnesium yields [(HPz(Tp))4Mg(Pz(Tp))2] (3b), which is stabilized in the solid state by intramolecular N-H···N···H-N hydrogen bridges. The degradation of [Ae{C(Pz(R))3}2] (R = Ph and Tp) has been studied by quantum chemical methods, the results of which propose an intermediate complex of the nature [{(Pz(R))2C}2Ca{Pz(R)}2]; thereafter, the singlet carbenes ([:C(Pz(R))2]) dimerize in the vicinity of the alkaline earth metal to tetrapyrazolylethene, which is liberated from the coordination sphere as a result of it being a very poor ligand for an s-block metal ion.

Synthesis, Characterization, and Reactivity of Lanthanide Amides Incorporating Neutral Pyrrole Ligand. Isolation and Characterization of Active Catalyst for Cyanosilylation of Ketones

A series of lanthanide amido complexes incorporating a neutral pyrrole ligand were synthesized and characterized, and their catalytic activities were studied. Treatment of [(Me3Si)2N]3Ln(μ-Cl)Li(THF)3 with 1 equiv of [(2,5-Me2C4H2N)CH2CH2] 2NH (1) in toluene afforded the corresponding lanthanide amides with the formula [η5:η1-(2,5-Me2C4H2N)CH2CH2]2NLn[N(SiMe3)2]2 (Ln = La (2), Nd (3)). Reaction of 2 or 3 with N,N′-dicyclohexylcarbodiimide (CyN═C═NCy) gave the carbodiimide selectively inserted into the appended Ln–N bond products formulated as CyNC{[N,N-(2,5-Me2C4H2N)CH2CH2]2N}NCyLn[N(SiMe3)2]2 (Ln = La (4), Nd (5)). Reactions of the lanthanide amides with Me3SiCN were also examined. A mixed reaction of [(Me3Si)2N]3La(μ-Cl)Li(THF)3, [(2,5-Me2C4H2N)CH2CH2]2NH (1), and Me3SiCN in toluene at room temperature produced the novel cyano bridged dinuclear lanthanum complex η5:η1:η3-[(2,5- Me2C4H2NCH2CH2)2N]La[N(SiMe3)2](μ-CN)La[N(SiMe3)2]3 (6). The stoichiometric reactions of lanthanide amides 2 or 3 with Me3SiCN produced the novel trinuclear lanthanum and neodymium complexes {(η5:η1-[(2,5-Me2C4H2NCH2CH2)2N]Ln[N(SiMe3)2](μ-CN)}3 (Ln = La (7), Nd (8)) through selective σ-bond metathesis reaction of the terminal Ln–N (N(SiMe3)2) bond with the Si–C bond of Me3SiCN. On the basis of the stoichiometric reactions of complexes 2, or 3 with Me3SiCN, complexes 2, 3, 4, 5, 7, and 8 as catalysts for cyanosilylation of ketones were investigated. Results indicated that these complexes displayed a high catalytic activity on addition of Me3SiCN to ketones, and the activity of the complexes has the order of 7 ∼ 8 > 2 ∼ 3 ∼ 4 ∼ 5. Thus, complex 7 or 8 was proposed as the active catalyst in the catalytic reaction for the precatalysts of 2 and 3.

β-diiminato titanium complexes with varying fluorine substitution patterns on the N-aryl moiety: probing the effect of ligand substitution on ethylene polymerization

A series of six mono β-diiminato titanium complexes with varying fluorine-substitution patterns on the iminophenyl moiety were designed and synthesized, and the ethylene polymerization activities were studied with modified methylaluminoxane (MMAO) as cocatalyst. The introduction of fluorine substituents significantly increased the catalytic activity of the β-diiminato titanium complexes compared with their alkyl-substituted counterparts. Furthermore, both the position and the amount of fluorine substitution greatly influenced the catalytic behavior. The activity was increased when the ortho-positions of the N-aryl were substituted by fluorine, and the more ortho-positions were substituted, the higher the activity. All of the three o-fluoro substituted complexes (2a, 2e and 2f) exhibited very high activity (up to 106gmol−1 h−1 atm−1); whereas the m- and p-fluoro derivatives (2b and 2c) were much less active. The high activity of the o-fluoro-substituted complexes is suggested to be due to the formation of non-covalent interactions between the o-fluorine atom and the ethylene monomer, which may assist in the enrichment and coordination of ethylene to the central metal, thus increase the catalytic activity.

Homo- and Heteroligated Salicylaldiminato Titanium Complexes with Different Substituents Ortho to the Phenoxy Oxygens for Ethylene and Ethylene/1-Hexene (Co)polymerization

A series of homoligated (1c–1e) and heteroligated (2a–2e) salicylaldiminato titanium dichloride complexes with different substituents ortho to the phenoxy oxygens were efficiently prepared. X-ray diffraction studies on these new dichloride complexes 2b, 2d, and 2e reveal a distorted octahedral coordination of the central metal. In the presence of dried methylaluminoxane, all the complexes exhibit high ethylene polymerization productivities. Surprisingly, complex 1d incorporating an o-(trimethylsilyl)ethynyl group displays the highest activity [5.26 × 103 kg of polyethylenes (mol Ti)−1 h–1]. In ethylene/1-hexene copolymerization, the heteroligated complexes 2a–2e display improved activities and intermediate incorporation ability compared with their homoligated counterparts 1a–1f. The activity and incorporation ability for 1-hexene are highly dependent on the nature of the ortho-substituents. Among them, (trimethylsilyl)ethynyl-substituted precatalyst (1d) achieves the highest incorporation ratio (27.3 mol %), while ethynyl-substituted precatalyst (2c) achieves the highest copolymerization activity [2.89 × 103 kg of copolymers (mol Ti)−1 h–1].

Enantioselective Divergent Synthesis of (−)‐cis‐α‐ and (−)‐cis‐γ‐Irone by Using Wilkinson’s Catalyst

A simple, efficient synthesis is reported for (-)-cis-α- and (-)-cis-γ-irone, two precious constituents of iris oils, in ≥99 % diastereomeric and enantioselective ratios. The two routes diverge from a common intermediate prepared from (-)-epoxygeraniol. Of general interest in this approach is the installation of the enone moiety of irones through a NHCAu(I) -catalyzed Meyer-Schuster-like rearrangement of a propargylic benzoate and the use of Wilkinson's catalyst for the stereoselective hydrogenation of a prostereogenic exocyclic double bond to secure the critical cis stereochemistry of the alkyl groups at C2 and C6 of the irones. The stereochemical aspects of this reaction are rationally supported by DFT calculation of the conformers of the substrates undergoing the hydrogenation and by a modeling study of the geometry of the rhodium η(2) complexes involved in the diastereodifferentiation of the double bond faces. Thus, computational investigation of the η(2) intermediates formed in the catalytic cycle of prostereogenic alkene hydrogenation by using Wilkinson's catalyst could be highly predictive of the stereochemistry of the products.

Synthesis, characterization, cytotoxicity of mixed ligand complexes of palladium(II) with dipyrido[3,2-d:2',3'-f]quinoxaline/dipyrido[3,2-a:2',3'-c](6,7,8,9-tetrahydro)phenazine and 4-toluensulfonyl-L-amino acid dianion.

Ten novel palladium(II) complexes with dipyrido[3,2-d:2',3'-f]quinoxaline (Dpq)/dipyrido[3,2-a:2',3'-c](6,7,8,9-tetrahydro)phenazine (Dpqc) and 4-toluensulfonyl-L-amino acid dianion, [Pd(Dpq)(TsvalNO)]·H2O (1a), [Pd(Dpq)(TsileNO)]·H2O (1b), [Pd(Dpq)(TsserNO)] (1c), [Pd(Dpq)(TsthrNO)]·1.5H2O (1d), [Pd(Dpq)(TsleuNO)]·0.5H2O (1e), [Pd(Dpq)(TspheNO)] (1f), [Pd(Dpqc)(TsvalNO)] (2a), [Pd(Dpqc)(TsileNO)] (2b), [Pd(Dpqc)(TsserNO)]·H2O (2c) and [Pd(Dpqc)(TsthrNO)]·0.5H2O (2d) have been synthesized and characterized by elemental analysis, IR, UV, (1)H NMR and mass spectrometry techniques. Crystal structure of the complex 1f has been determined by X-ray diffraction. The cytotoxicity was tested by MTT assay. The results indicated that the complexes 1a and 2a showed better cytotoxicity than cisplatin against MCF-7. The complex 1e had higher cytotoxicity than cisplatin against K562. Both the N donating ligands and the amino acid have important effects on the cytotoxicity.

Cobalt Complexes Containing Pendant Amines in the Second Coordination Sphere as Electrocatalysts for H2 Production

A series of heteroleptic 17e cobalt complexes, [CpCoII(PtBu2NPh2)](BF4), [CpC6F5CoII(PtBu2NPh2)](BF4), and [CpC5F4NCoII(PtBu2NPh2)](BF4) (where PtBu2NPh2 = 1,5-diphenyl-3,7-di-tert-butyl-1,5-diaza-3,7-diphosphacyclooctane, CpC6F5 = C5H4(C6F5), and CpC5F4N = C5H4(C5F4N)) were synthesized, and the structures of all three were determined by X-ray crystallography. Electrochemical studies showed that the CoIII/II couple of [CpC5F4NCoII(PtBu2NPh2)]+ appears 250 mV positive of the CoIII/II couple of [CpCoII(PtBu2NPh2)]+ as a result of the strongly electron withdrawing perfluoropyridyl substituent on the Cp ring. Reduction of these paramagnetic CoII complexes by KC8 led to the diamagnetic 18e complexes CpCoI(PtBu2NPh2), CpC6F5CoI(PtBu2NPh2), and CpC5F4NCoI(PtBu2NPh2), which were also characterized by crystallography. Protonation of these neutral CoI complexes led to the CoIII hydrides [CpCoIII(PtBu2NPh2)H](BF4), [CpC6F5CoIII(PtBu2NPh2)H](BF4), and [CpC5F4NCoIII(PtBu2NPh2)H](BF4), and crystal structures of each of...

Ultrafast infrared studies of the role of spin states in organometallic reaction dynamics.

The importance of spin state changes in organometallic reactions is a topic of significant interest, as an increasing number of reaction mechanisms involving changes of spin state are consistently being uncovered. The potential influence of spin state changes on reaction rates can be difficult to predict, and thus this class of reactions remains among the least well understood in organometallic chemistry. Ultrafast time-resolved infrared (TRIR) spectroscopy provides a powerful tool for probing the dynamics of spin state changes in organometallic catalysis, as such processes often occur on the picosecond to nanosecond time scale and can readily be monitored in the infrared via the absorptions of carbonyl reporter ligands. In this Account, we summarize recent work from our group directed toward identifying trends in reactivity that can be used to offer predictive insight into the dynamics of coordinatively unsaturated organometallic reaction intermediates. In general, coordinatively unsaturated 16-electron (16e) singlets are able to coordinate to solvent molecules as token ligands to partially stabilize the coordinatively unsaturated metal center, whereas 16e triplets and 17-electron (17e) doublets are not, allowing them to diffuse more rapidly through solution than their singlet counterparts. Triplet complexes typically (but not always) undergo spin crossover prior to solvent coordination, whereas 17e doublets do not coordinate solvent molecules as token ligands and cannot relax to a lower spin state to do so. 16e triplets are typically able to undergo facile spin crossover to yield a 16e singlet where an associative, exothermic reaction pathway exists. The combination of facile spin crossover with faster diffusion through solution for triplets can actually lead to faster catalytic reactivity than for singlets, despite the forbidden nature of these reactions. We summarize studies on odd-electron complexes in which 17e doublets were found to display varying behavior with regard to their tendency to react with 2-electron donor ligands to form 19-electron (19e) adducts. The ability of 19e adducts to serve as reducing agents in disproportionation reactions depends on whether the excess electron density localized at the metal center or at a ligand site. The reactivity of both 16e and 17e complexes toward a widely used organic nitroxyl radical (TEMPO) are reviewed, and both classes of complexes generally react similarly via an associative mechanism with a low barrier to these reactions. We also describe recent work targeted at unraveling the photoisomerization mechanism of a thermal-solar energy storage complex in which spin state changes were found to play a crucial role. Although a key triplet intermediate was found to be required for this photoisomerization mechanism to proceed, the details of why this triplet is formed in some complexes (those based on ruthenium) and not others (those based on iron, molybdenum, or tungsten) remains uncertain, and further exploration in this area may lead to a better understanding of the factors that influence intramolecular and excited state spin state changes.

Chiral nickel(II) and palladium(II) catalysts bearing strong electron‐withdrawing fluorine groups: synthesis, characterization and their application in catalytic polymerization for ethylene and styrene

A series of new chiral and achiral nickel(II) and palladium(II) complexes, {bis[N,N′‐(2,6‐diethyl‐4‐naphthylphenyl)imino]‐1,2‐dimethylethane}dibromonickel 3a, {bis[N,N′‐(4‐fluoro‐2‐methyl‐6‐sec‐phenethylphenyl)imino]‐1,2‐dimethylethane}dibromonickel rac‐(RS)‐3b, {bis[N,N′‐(4‐fluoro‐6‐sec‐phenethylphenyl)imino]‐1,2‐dimethylethane}dibromonickel rac‐(RR/SS)‐3c and {bis[N,N′‐(4‐fluoro‐6‐sec‐phenethylphenyl)imino]‐1,2‐dimethylethane}dichloropalladium rac‐(RR/SS)‐3d were successfully synthesized and characterized. The molecular structures of representative ligand rac‐(RS)‐2b, nickel complex 3a, rac‐(RR/SS)‐3c and palladium complex rac‐(RR/SS)‐3d were determined by X‐ray crystallography. The structures of complexes 3a and rac‐(RR/SS)‐3c have pseudo‐tetrahedral geometry about the nickel center, showing C2 molecular symmetry. However, the structure of palladium complex rac‐(RR/SS)‐3d has pseudo‐square planar geometry about the palladium center, showing C2 molecular symmetry. Complex 3e {bis[N,N′‐(2,6‐dimethylphenyl)imino]‐1,2‐dimethylethane}dibromonickel was also synthesized for comparison. Nickel complex rac‐(RS)‐3b bearing strong electron‐withdrawing fluorine group in the para‐aryl position and a chiral sec‐phenethyl group in the ortho‐aryl position of the ligand (one methyl group in the ortho‐aryl position) displays the highest catalytic activity for ethylene and styrene polymerization, and produced highly branched polyethylene and syndiotactic‐rich polystyrene. However, palladium complex rac‐(RR/SS)‐3d shows low catalytic activity for ethylene and styrene polymerization due to the poor leaving group, Cl, attached to palladium and the unfavorable molecular structure. Copyright © 2014 John Wiley & Sons, Ltd.

Synthesis, characterization, and 1,3-butadiene polymerization studies of Co(II), Ni(II), and Fe(II) complexes bearing 2-(N-arylcarboximidoylchloride)quinoline ligand

A series of Co(II), Ni(II), and Fe(II) complexes supported by quinolinylimidoylchloride ligands [2-(N-ArN=CCl)C9H6N]MtBr2 (Ar=2,6-iPr2C6H3, M=Co (1a), Mt=Ni (2a), Mt=Fe (3a); Ar=2,6-Et2C6H3, Mt=Co (1b), Mt=Ni (2b), Mt=Fe (3b); Ar=2,6-Me2C6H3, Mt=Co (1c), Mt=Ni (2c), Mt=Fe (3c); Ar=C6H5, Mt=Co (1d), Mt=Ni (2d), Mt=Fe (3d); Ar=4-ClC6H4, Mt=Co (1e), Mt=Ni (2e), Mt=Fe (3e); Ar=4-OMe-C6H4, Mt=Co (1f), Mt=Ni (2f), Mt=Fe (3f)) were synthesized. The solid structure of ligand c, complexes 1e and 2a were characterized by single crystal X-ray analysis, showing that 1e was tetra-coordinate with a distorted tetrahedral geometry and 2a was penta-coordinate with a distorted trigonal bipyramid configuration. The imidoylchloride Co(II) and Ni(II) complexes (1a and 2a) activated by ethylalumium sesquichloride (EASC) displayed higher activities than did the aldimine-based Co(II) and Ni(II) complex (1A and 2A). The Co(II)-, Ni(II)-, and Fe(II)-based complexes exhibited different stereospecificities and afforded polybutadienes with different molecular weights due to the nature of the metal centre and the environment of the ligand. The imidoylchloride Co(II) complexes exhibited much better temperature tolerance, affording polymer in a high yield of 93.4% even at 80°C.

Interconversion of η3-H2SiRR′ σ-Complexes and 16-Electron Silylene Complexes via Reversible H–H or C–H Elimination

Solid samples of η(3)-silane complexes [PhBP(Ph)3]RuH(η(3)-H2SiRR') (R,R' = Et2, 1a; PhMe, 1b; Ph2, 1c, MeMes, 1d) decompose when exposed to dynamic vacuum. Gas-phase H2/D2 exchange between isolated, solid samples of 1c-d3 and 1c indicate that a reversible elimination of H2 is the first step in the irreversible decomposition. An efficient solution-phase trap for hydrogen, the 16-electron ruthenium benzyl complex [PhBP(Ph)3]Ru[η(3)-CH2(3,5-Me2C6H3)] (3) reacts quantitatively with H2 in benzene via elimination of mesitylene to form the η(5)-cyclohexadienyl complex [PhBP(Ph)3]Ru(η(5)-C6H7) (4). This H2 trapping reaction was utilized to drive forward and quantify the elimination of H2 from 1b,d in solution, which resulted in the decomposition of 1b,d to form 4 and several organosilicon products that could not be identified. Reaction of {[PhBP(Ph)3]Ru(μ-Cl)}2 (2) with (THF)2Li(SiHMes2) forms a new η(3)-H2Si species [PhBP(Ph)3]Ru[CH2(2-(η(3)-H2SiMes)-3,5-Me2C6H2)] (5) which reacts with H2 to form the η(3)-H2SiMes2 complex [PhBP(Ph)3]RuH(η(3)-H2SiMes2) (1e). Complex 1e was identified by NMR spectroscopy prior to its decomposition by elimination of Mes2SiH2 to form 4. DFT calculations indicate that an isomer of 5, the 16-electron silylene complex [PhBP(Ph)3]Ru(μ-H)(═SiMes2), is only 2 kcal/mol higher in energy than 5. Treatment of 5 with XylNC (Xyl = 2,6-dimethylphenyl) resulted in trapping of [PhBP(Ph)3]Ru(μ-H)(═SiMes2) to form the 18-electron silylene complex [PhBP(Ph)3]Ru(CNXyl)(μ-H)(═SiMes2) (6). A closely related germylene complex [PhBP(Ph)3]Ru[CN(2,6-diphenyl-4-MeC6H2)](H)(═GeH(t)Bu) (8) was prepared from reaction of (t)BuGeH3 with the benzyl complex [PhBP(Ph)3]Ru[CN(2,6-diphenyl-4-MeC6H2)][η(1)-CH2(3,5-Me2C6H3)] (7). Single crystal XRD analysis indicated that unlike for 6, the hydride ligand in 8 is a terminal hydride that does not engage in 3c-2e Ru-H → Ge bonding. Complex 1b is an effective precatalyst for the catalytic Ge-H dehydrocoupling of (t)BuGeH3 to form ((t)BuGeH2)2 (85% yield) and H2.

{Bis[N,N′-(2-alkyl-6-sec-phenethylphenyl)imino]-1,2-dimethylethane}dibromonickel complexes bearing chiral sec-phenethyl groups: Synthesis, characterization and their application in catalytic polymerization for ethylene and styrene

A series of new chiral and achiral nickel (II) complexes, {bis[N,N′-(2-methyl-6-sec-phenethylphenyl)imino]-1,2-dimethylethane}dibromonickel rac-(RR/SS)-3a, {bis[N,N′-(4-isopropyl-2-sec-phenethylphenyl)imino]-1,2-dimethylethane}dibromonickel rac-(RSRS)-3b, {bis[N,N′-(2-methyl-4,6-di(sec-phenethyl)phenyl)imino]-1,2-dimethylethane}dibromonickel rac-(RSRS)-3c, and {bis[N,N′-(2,6-diisopropyl-4-(p-methylphenyl)phenyl)imino]-1,2-dimethylethane}dibromonickel 3d, were synthesized and characterized. The molecular structures of the representative ligand rac-(RSRS)-2c, complex rac-(RR/SS)-3a, complex rac-( RSRS)-3b, and complex 3d were determined by X-ray crystallography. Complex 3e {bis[N,N′-(2,6-dimethylphenyl)imino]-1,2-dimethylethane}dibromonickel was also synthesized for comparison. These complexes, activated by diethylaluminum chloride (DEAC) were tested in the polymerization of ethylene and styrene under mild conditions. Complex rac-(RSRS)-3c bearing one ortho-methyl group and two chiral bulky sec-phenethyl groups in the ortho- and para-aryl position of the ligand, activated by diethylaluminum chloride (DEAC) shows highly catalytic activity for the polymerization of ethylene [5.56 × 106 g PE/(mol Ni h bar)] and produced branched polyethylene (75 methyl, 9 ethyl, 5 propyl and 19 butyl or longer branches/1000 C at 40 °C). Interestingly, complex rac-(RSRS)-3c also displays highly catalytic activity (3.62 × 105 g polystyrene/(mol Ni h)) for styrene polymerization, and could produce syndiotactic-rich polystyrene (stereo-triad distributions: rr, 66.2%; mr, 18.8%; mm, 15.0%; stereo-diad distributions: r, 75.6%; m, 24.4% at 70 °C). The achiral catalyst 3d gave nearly atactic polystyrene (stereo-triad distributions: rr, 37.0%; mr, 32.7%; mm, 30.3%; stereo-diad distributions: r, 53.4%; m, 46.6% at 70 °C).

Tuning the Luminescent Properties of Pt(II) Acetylide Complexes through Varying the Electronic Properties of N-Heterocyclic Carbene Ligands

This Article reports the synthesis, structural characterization, electrochemistry, and photophysical investigations of five groups of luminescent Pt(II) alkynyl complexes bearing N-heterocyclic carbene (NHC) ligands with varying electronic properties. Complexes of the type [Pt(pmdb)(C≡CR)2] 1a-c, [Pt(pm2tz)(C≡CR)2] 2a-d, [Pt(pm3tz)(C≡CR)2] 3a-c, [Pt(ppim)(C≡CR)2] 4(a, b, e), and [Pt(ppbim)(C≡CR)2] 5(a, b, e), where pmdb =1,1'-dipentyl-3,3'-methylene-dibenzimidazoline-2,2'-diylidene, pm2tz = 1,1'-dipentyl-3,3'-methylene-di-1,2,4-triazoline-5,5'-diylidene, pm3tz = 1,1'-dipentyl-3,3'-methylene-di-1,3,4-triazoline-5,5'-diylidene, ppim = 3-pentyl-1-picolylimidazoline-2-ylidene, and ppbim = 3-pentyl-1-picolylbenzimidazoline-2-ylidene, and R = 4-C6H4F, C6H5, 4-C6H4OMe, SiMe3, and 4-C6H4N(C6H5)2, were prepared, and the consequences of the electronic properties of the NHC ligands on the phosphorescent emission efficiencies were studied. Moreover, the emission quantum efficiencies of the previously reported complexes [Pt(pmim)(C≡CR)2] where pmim = 1,1'-dipentyl-3,3'-methylene-diimidazoline-2,2'-diylidene and R = 4-C6H4F 6a, C6H5 6b, and 4-C6H4OMe 6c were also recorded in neat solid and in 10 wt % PMMA film. The square planar coordination geometry with the alkynyl ligands in cis configuration was corroborated for selected complexes by single crystal X-ray diffraction studies. The observed moderate difference in emission efficiencies of the bis-carbene complexes 6a-c, 1a-c, 2a-c, and 3a-c in conjunction with the decreasing electron-donating nature of the NHC ligands, pmim > pmdb > pm2tz ≈ pm3tz, can be attributed to the slight modification of the triplet emission parentage among the different complexes. The quantum efficiencies of complexes 4(a, b) and 5(a, b) bearing pyridyl-NHC ligand were significantly low in comparison to the bis-carbene complexes owing to the significant change in the charge transfer character of the triplet manifold. Complexes 4e and 5e bearing diarylamine phenylacetylenes display high ϕem of 27% and 33% in 10 wt % PMMA film, respectively.

Half sandwich ruthenium(II) hydrides: hydrogenation of terminal, internal, cyclic and functionalized olefins.

Bis(1,2,3-triazolylidene) silver(I) complex 1a was reacted with [RuCl2(p-cymene)]2 to give the ruthenium complex [PhCH2N2(NMe)C2(C6H4CF3)]RuCl2(p-cymene) (2a) as major product in addition to the minor C(sp(2))-H activated product [PhCH2N2(NMe)C2(C6H3CF3)]RuCl(p-cymene) (2a'). Similar ruthenium complexes 2b, 2c, 2d and 2e with general formula RuCl2(p-cymene)(NHC) (NHC = MesCH2N2(NMe)C2Ph 2b, PhCH2N2(NMe)C2Ph 2c, TripCH2N2(NMe)C2Ph 2d, IMes 2e) were also synthesized. Subsequent reaction of Me3SiOSO2CF3 with 2a and 2b resulted in cationic ruthenium species [(PhCH2N2(NMe)C2(C6H4CF3))RuCl(p-cymene)][OSO2CF3] (3a) and [(MesCH2N2(NMe)C2Ph)RuCl(p-cymene)][OSO2CF3] (3b), respectively. Complexes 3a and 3b dissolved in CD3CN to give [(PhCH2N2(NMe)C2(C6H4CF3))RuCl(CD3CN)(p-cymene)][OSO2CF3] (4a) and [(MesCH2N2(NMe)C2Ph)RuCl(CD3CN)(p-cymene)][OSO2CF3] (4b), respectively. Cationic ruthenium species 4a and 4b failed to show catalytic activity towards hydrogenation of olefins. Ruthenium(II) complexes 2b-e with the general formula RuCl2(p-cymene)(NHC) were reacted with Et3SiH to generate a series of ruthenium(II) hydrides 5b-e. These compounds 5b-e are effective catalysts for the hydrogenation of terminal, internal and cyclic and functionalized olefins.

Bimetallic ruthenium complexes bridged by divinylphenylene bearing oligo(ethylene glycol)methylether: synthesis, (spectro)electrochemistry and the lithium cation effect

A series of 1,4-disubstituted ruthenium-vinyl complexes, (E,E)-[{(PMe3)3(CO)ClRu}2(μ-HC=CH-Ar-CH=CH)], in which the 1,4-diethenylphenylene bridge bears two oligo(ethylene glycol)methyl ether side chains at different positions (2,5- and 2,3-positions), were prepared. The respective products were characterized by elemental analyses and NMR spectroscopy. The structures of complexes 1b and 1e were established by X-ray crystallography. The electronic properties of the complexes were investigated by cyclic voltammetry, and IR and UV-vis/NIR spectroscopies. Electrochemical studies showed that the 2,5-substituents better stabilized the mixed-valence states; the electrochemical behavior was greatly affected by lithium cations, especially complex 1g with 2,3-substituents, which was further supported by IR and UV-vis/NIR spectra changes. Spectroelectrochemical studies showed that the redox chemistry was dominated by the non-innocent character of the bridging fragment.

Synthesis, structures, and norbornene polymerization behavior of C(sp³), N-chelated palladacycles bearing o-aryloxide-N-heterocyclic carbene ligands.

Treatment of the o-hydroxyaryl imidazolium pro-ligands (2-OH-3,5-tBu2C6H2)(R)(C3H3N2)(+)Br(-) [R = Mes (1a), Ph (1b), iPr (1c), Me (1d)] with Ag2O afforded the corresponding silver complexes 2a-d. Subsequent metal-exchange reactions of 2a-d with [Pd(OAc)(8-Me-quin-H)]2 (3) yielded the desired C(sp(3)), N-chelated and o-aryloxide-NHC-ligated palladacycle complexes 4a-d in 60-80% yields. When the N-tert-butyl substituted o-hydroxyaryl imidazolium pro-ligand 1e reacted with 3 in the presence of K2CO3 in dioxane, the palladacycle complex 4e, in which the NHC adopted an abnormal binding (C4-bonding), was obtained in 20% yield. All these complexes were fully characterized using (1)H and (13)C NMR spectra, high-resolution mass spectrometry (HRMS), and elemental analysis. Single-crystal X-ray diffraction analysis results further confirmed the molecular structures of 4a-c and the abnormal binding of NHC in 4e. With methylaluminoxane (MAO) as the cocatalyst these palladacycles showed excellent catalytic activities of up to 10(7) g of PNB (mol of Pd)(-1) h(-1) in the addition polymerization of norbornene.