Unsymmetrical Ligand Research Articles

Solid‐state and Computational Study of “Venus fly‐trap” Geometric Parameters for 1,5‐Cyclooctadiene in PdII and PtII β‐Enaminonato Complexes

The cod ligand (cis,cis‐1,5‐cyclooctadiene) can be superficially considered to mimic similarities in spatial behavior of a leaf of the Venus fly‐trap (Dionaea muscipula). Thus, the synthesis of an unsymmetrical bidentate trans ligand (N,O‐donor atoms) based on the β‐enaminonate backbone is introduced to evaluate the electronic and steric influence on the structural behavior of the cod ligand when coordinated to a square planar transition metal. A range of platinum(II) / palladium(II) complexes of the type [M(cod)(N,O‐Bid)]A (M = PtII, PdII; β‐enaminonato ligand (N,O‐Bid) = NH‐acac, NMe‐acac, NPh‐acac; A = BF4–, PF6–) is reported. The complexes were fully characterized, including by detailed X‐ray structural investigations. Theoretical calculations on the [M(cod)(N,O‐Bid)]+ complexes for the complete nickel triad are also described and the structural behavior of the cod ligand critically evaluated. The influence of the variation of the β‐enaminonato ligands on the coordination arrangement of the cod was investigated and found that no significant changes to the M–C and C=C bond lengths were observed. The Venus fly‐trap jaw angle (ψ), however, varies by ca. 8° and the twist angle (τ) by ca. 10°, whereas the cod bite angle (χ), as well as the β‐enaminonato ligand bite angle (N–M–O; θ) both remain virtually constant. Calculated spectroscopic tendencies within the Ni‐triad are also included.

An unsymmetrical tritopic pyrazole carboxylate ligand based porous Cd(II) MOF sensor for acetone molecule

A Cd(II) based novel 3D porous MOF, {[Cd4(L)4(NO3)3(H2O)3]∙8DMF∙H2O∙NO3}n (1) (where, L = 4-(3,5-di(pyridin-4-yl)-1H-pyrazol-1-yl)benzoic acid) is reported. Compound 1 features open N sites and 6,3 connected net with ant/anatase topology having nano sized cavities in the 2D sheet structure which are masked by the adjacent layers stacked in a slipped manner in 3D packing. The open voids in 1 are occupied by DMF and water solvent molecules that constitute 46% of the total volume of crystal. Compound 1 exhibits selective H2O vapor adsorption over methanol and ethanol solvents. Its solid state luminescent property demonstrates that it can selectively detect acetone molecules on the basis of fluorescence quenching mechanism among several other solvent molecules.

Synthesis, structure and magnetic properties of three CuII2LnIII complexes (Ln = Pr, Nd and Sm) with an unsymmetrical Schiff base ligand

Three heterometallic trinuclear complexes of general formula, [{(CH3CN)CuL}2(µ-NO3)2Ln(NO3)] [Ln = Pr (1), Nd (2) and Sm (3)] have been synthesized by reacting a neutral metalloligand [CuL], derived from a N2O2 donor unsymmetrically di-condensed di-Schiff base, H2L (where H2L = N-α-methylsalicylidene-N΄-salicylidene-1,3-propanediamine) with the respective lanthanide nitrates in 2:1 ratios. X-ray single-crystal structure reveals that these isomorphic complexes (1–3) possess C2-symmetric trinuclear units where two terminal metalloligands are coordinated to the central Ln(III) ion in transoid manner. In all three complexes, distorted tetradecahedron coordination geometry is formed around the Ln(III) ion by four μ2-phenoxido oxygen atoms from two (CuL) units and three chelating nitrato coligands. The two terminal Cu(II) ions possess distorted octahedral geometry. The dc magnetic susceptibilities and field dependent magnetization measurements of all three complexes reveal the occurrence of antiferromagnetic interactions between Cu(II) and Ln(III) ions.

Palladium complexes with two unsymmetrical Schiff base ligands: Highly active catalyst for activation of chloroarenes in Suzuki-Miyaura reaction

Palladium complexes with two unsymmetrical Schiff base ligands: Highly active catalyst for activation of chloroarenes in Suzuki-Miyaura reaction

Selective Synthesis of a Series of Isostructural MII CuI Heterobimetallic Complexes Spontaneously Assembled by an Unsymmetrical Naphthyridine-Based Ligand.

Metal-metal cooperation is integral to the function of many enzymes and materials, and model complexes hold enormous potential for providing insights into the capabilities of analogous multimetallic cores. However, the selective synthesis of heterobimetallic complexes still presents a significant challenge, especially for systems that hold the metals in close proximity and feature open or reactive coordination sites for both metals. To address this issue, a rigid, naphthyridine-based dinucleating ligand featuring distinct binding environments was synthesized. This ligand enables the selective synthesis of a series of MII CuI bimetallic complexes (M=Mn, Fe, Co, Ni, Cu, Zn), in which each metal center exclusively occupies its preferred binding pocket, from simple chloride salts. The precision of this selectivity is evident from cyclic voltammetry, ESI-MS and anomalous X-ray diffraction measurements.

Ni(II) Complex of N2O3 Donor Unsymmetrical Ligand and Its Use for the Synthesis of NiII-MnII Complexes of Diverse Nuclearity: Structures, Magnetic Properties, and Catalytic Oxidase Activities.

A new mononuclear Ni(II) complex [NiL] (1) of an unsymmetrically dicondensed N2O3 donor ligand, H2L ( N-α-methylsalicylidene- N'-3-methoxysalicylidene-1,3-propanediamine), has been synthesized. Complex 1 on reaction with Mn(ClO4)2·6H2O and NaN3 in different molar ratios yielded three novel heterometallic NiII-MnII complexes, [(NiL)2Mn(N3)](ClO4) (2), [(NiL)2Mn2(N3)2(μ1,1-N3)2(CH3OH)2] (3), and [{(NiL)2Mn}2(μ1,3-N3)(H2O)]·(CH3OH),(ClO4)3 (4). The single crystal structure analyses show a trinuclear NiII2MnII structure for complex 2 and a tetranuclear NiII2MnII2 structure where two dinuclear NiIIMnII units are connected via μ1,1-azido and phenoxido bridges for complex 3. Complex 4 possesses a hexanuclear structure where two trinuclear NiII2MnII units are connected via a μ1,3-azido bridge. The temperature-dependent dc molar magnetic susceptibility measurements reveal that complexes 3 and 4 are antiferromagnetically coupled with the exchange coupling constants ( J) of -4.97, -0.14, -0.55 cm-1 for 3 and -3.94 cm-1 for 4. All complexes 2-4 show biomimetic catalytic oxidase activities. For catecholase like activity, the turnover numbers ( Kcat) are 768, 1985, and 2309 h-1 for complexes 2-4, respectively, whereas for phenoxazinone synthase like activity, the turnover numbers are 3240, 3360, and 13 248 h-1 for complexes 2-4, respectively. This difference in catalytic efficiencies is attributed to the variations in structures of the complexes and formation of active NiII-MnII species in solution during catalysis. The mass spectral analyses suggest the probable intermediate formation and cyclic voltammetry measurement suggest the reduction of Ni(II) to Ni(I) during catalytic reaction. The very high catalytic efficiencies for aerial dioxygen activation of all these heterometallic complexes as well as the highest activity of 4 is attributed to the coordinatively unsaturated penta-coordinated geometry or hexa-coordinated geometry with a solvent water molecule around Mn(II).

Designing Eu-β-diketonate complexes as a support of ionic liquid crystals (ILCs) with additional luminescent properties

Here we describe the preparation, characterisation, liquid crystal properties and photophysical studies of new potassium salts of tetrakis(β-diketonate)europium(III) complexes based on long-chained symmetrical and unsymmetrically substituted 1,3-dialkyloxyphenyl-β-diketones ligands, K[Eu(OOR(n)R(m))4] (R(n) = OC6H4OCnH2n+1; R(m) = OC6H4OCmH2m+1; n = m = 8, 10, 12, 14, 16; n = 4, 8, m = 12, 16; n = 12, m = 16). All compounds exhibit mesomorphic and luminescence behaviour, regardless the presence of symmetrical or unsymmetrical ligands. It has been shown that the shortest molecular lengths, established by the summation of the two alkyl chains at the substituents of the β-diketonate ligand, give rise to more effective mesophase transition temperatures, while the asymmetry favours higher clearing temperatures. Related to the ionic salts based on long-chained pirazolium cations [H2pzR(n)]+ (R(n) = OC6H4OCnH2n+1; n = 4, 6, 8, 10, 12, 14, 16, 18) and tetrakis(1,3-bis(methoxyphenyl)propane-1,3-dionate)europium(III) as anion, they have also been studied and proved to be luminescent materials. By contrast, none of them was found to be mesomorphic. Therefore, the strategically increased chain length at the cation did not show to be effective for achieving liquid crystal properties. Integration of one of these luminescent europium complexes onto a polymeric PMMA matrix was positively evaluated towards its use as a temperature sensor and fluoride or cyanide ion sensor.

An Unsymmetric Ligand with a N5O2 Donor Set and Its Corresponding Dizinc Complex: A Structural and Functional Phosphoesterase Model

To mimic the active sites of the hydrolytic enzyme zinc phosphotriesterase, a new dinucleating unsymmetric ligand, PICIMP (2‐{[2‐hydroxy‐5‐methyl‐3‐({[(1‐methyl‐1H‐imidazol‐2‐yl)methyl](pyridin‐2‐ylmethyl)amino}methyl)benzyl][(1‐methyl‐1H‐imidazol‐2‐yl)methyl]amino}acetic acid), has been synthesized and characterized. The hydrolytic efficacy of the complex solution (PICIMP/ZnCl2 = 1:2) has been investigated using bis‐(2,4‐dinitrophenyl)phosphate (BDNPP), a DNA analogue substrate. Speciation studies were undertaken by potentiometric titrations at varying pH for both the ligand and the corresponding dizinc complex to elucidate the formation of the active hydrolysis catalyst; these studies reveal that the dinuclear zinc(II) complexes, [Zn2(PICIMP)]2+ and [Zn2(PICIMP)(OH)]+ predominate in solution above pH 4. The obtained pKa of 7.44 for the deprotonation of water suggests formation of a bridging hydroxide between the two ZnII ions. Kinetic investigations of BDNPP hydrolysis over the pH range 5.5–10.5 have been performed. The cumulative results indicate the hydroxo‐bridged dinuclear ZnII complex [Zn2(PICIMP)(µ‐OH)]+ as the effective catalyst. Density functional theory calculations were performed to investigate the detailed reaction mechanism. The calculations suggest that the bridging hydroxide becomes terminally coordinated to one of the zinc ions before performing the nucleophilic attack in the reaction.

Bond Dissociation Energies of Metallo-supramolecular Building Blocks: Insight from Fragmentation of Selectively Self-Assembled Heterometallic Metallo-supramolecular Aggregates.

A series of selectively self-assembled metallo-supramolecular square-like macrocycles with unsymmetric ditopic linkers and two different types of metal corners, i.e., {Pd(η3-2-Me-C3H4)} and {M(dppp)} with dppp = 1,3-bis(diphenylphosphino)propane and M = Pd2+ or Pt2+, have been studied in the gas phase using collision-induced dissociation. The aggregates show distinct fragmentation patterns determined by ligand length, i.e, aggregate size, and type of metal corner. Information on relative binding strength can be deduced. This is of particular interest for (methylallyl)Pd as a relatively new building block in metallo-supramolecular chemistry. The phosphane end of the unsymmetric ligand connected to (η3-2-Me-C3H4)Pd is bound significantly stronger than its pyridine end to (dppp)Pt and (dppp)Pd. These results are corroborated by DFT calculations.

Functional modeling of the MnCAT active site with a dimanganese(III) complex of an unsymmetrical polydentate N3O3 ligand

A new diMnIII complex, [Mn2L(OAc)2(H2O)](BPh4)·3H2O (1), obtained with the unsymmetrical N3O3-ligand H3L = 1-[N-(2-pyridylmethyl),N-(2-hydroxybenzyl)amino]-3-[N′-(2-hydroxybenzyl),N′-(benzyl)amino]propan-2-ol, has been prepared and characterized. The unsymmetrical hexadentate ligand L3− leads to coordination dissymmetry (dissimilar donor atoms) around each Mn ion (N2O4 and NO4(solvent), respectively) leaving one labile site on one of the two Mn ions that facilitates interaction of the metal center with H2O2, as in Mn catalase. 1 is able to catalyze H2O2 disproportionation in acetonitrile, with second-order rate constant kcat = 23.9(2) M−1 s−1. The accessibility of the MnII2 state and the closeness of the two one-electron reduction processes suggest 1 employs MnIII2/MnII2 oxidation states for catalysis.

Solvent-Induced Unsymmetric Salamo-Like Trinuclear NiII Complexes: Syntheses, Crystal Structures, Fluorescent and Magnetic Properties

Solvent-induced trinuclear NiII complexes, [{Ni(L)(MeOH)}2(OAc)2Ni]·2MeOH (1), [{Ni(L)(EtOH)}2(OAc)2Ni]·2H2O (2), [{Ni(L)(n-PrOH)}2(OAc)2Ni]·2H2O (3) and [{Ni(L)(i-PrOH)}2(OAc)2Ni] (4), have been prepared with an unsymmetric Salamo-like ligand H2L, and characterized via X-ray crystallography, FT-IR, UV-Vis and fluorescence spectra. In complexes 1, 2, 3 and 4, there are two ligand (L)2− moieties, two acetato ligands, two coordinated methanol, ethanol, n-propanol or i-propanol molecules, respectively, as well as other crystallizing solvent molecules. Two acetato ligands coordinated to the three NiII ions via usual Ni-O-C-O-Ni bridges, and four µ-phenoxo oxygen atoms coming from two [NiL(solvent)] units coordinate to the central NiII ions. Although different solvents are induced in the complexes, all the NiII ions are six-coordinated and adopt geometries of distorted octahedron. Magnetic measurements were performed on complex 2, an intramolecular antiferromagnetic interaction was observed between NiII ions and a simulation of the experimental data gives J = −2.96 cm−1 and g = 2.30.

The synthesis and investigation of different cobaloximines by spectroscopic methods

In the present work, firstly a novel monoxime (1) and unsymmetric dioxime ligand (LH2) (2) derived from 4-(4-hydroxyphenyl)-2-butanone as ketone was prepared under optimum conditions. Then, the cobaloxime complexes [(LH)2ClCoB] (B = neutral base: 4-DAP = 4-(dimethylamino)pyridine, 4-HP = 4-hydroxypyridine, 4-CP = 4-chloropyridine, 4-MP = 4-methylpyridine, 4-EP = 4-ethylpyridine, 4-TBP = 4-tert-butylpyridine and P = pyridine) (3–9) with respect to varied axial groups were synthesized in a two-necked round-bottom reaction flask by direct contact of dioxime ligand (2), and different neutral base without special requirement of any additional chemical process. The prepared dioxime ligand (2) and its cobaloxime complexes (3–9) were characterized by means of NMR, FT-IR, UV–Vis and LC-MS spectroscopy, melting point and magnetic susceptibility measurements as well as elemental analysis. It is noteworthy that the coordination chemistry of this cobaloxime complexes is versatile, which is closely related to the nature of the unsymmetric dioxime ligand (2) derived from 4-(4-hydroxyphenyl)-2-butanone, as indicated by the results of the corresponding spectroscopic studies. Also, the spectroscopic results demonstrated that the proposed cobaloxime complexes are a six-coordinated species and octahedral geometry.

Concurrently Improving the Thermal Stability and Activity of Ferrous Precatalysts for the Production of Saturated/Unsaturated Polyethylene

The five unsymmetrical ligands 2-[1-(2,6-dibenzhydryl-4-tert-butylphenylimino)ethyl]-6-[1-(arylimino)ethyl]pyridine (aryl = 2,6-Me2C6H3 (L1), 2,6-Et2C6H3 (L2), 2,6-iPr2C6H3 (L3), 2,4,6-Me3C6H2 (L4), 2,6-Et2-4-MeC6H2 (L5)) and the symmetrical ligand 2,6-bis(1-(2,6-dibenzhydryl-4-tert-butylphenylimino)ethyl)pyridine (L6) have been prepared and characterized by FT IR and 1H/13C NMR spectroscopy and elemental analysis. The treatment of L1–L6 with FeCl2·4H2O afforded the corresponding ferrous chloride complexes (Fe1–Fe6) in excellent yields. A distorted-square-pyramidal geometry with a τ5 value of 0.13 is a feature of the X-ray structure of Fe3; broad paramagnetically shifted peaks are revealed in the 1H NMR spectra for all the iron complexes in solution. On activation with either MAO or MMAO cocatalyst, all iron complexes displayed high activities with modest variations in activities at elevated temperature (up to 12.0 × 106, 12.4 × 106, 12.8 × 106, and 13.1 × 106 g of PE (mol of Fe)−1 h–1 at 50, 60, 70, and ...

Steric factors on unsymmetrical O-hydroxyaryl N-Heterocyclic carbene ligands prevailing the stabilization of single stereoisomer of bis-ligated titanium complexes

Bis-ligated titanium (IV) metal complexes supported by bidentate unsymmetrical o-hydroxyaryl-substituted N-heterocyclic carbene ligands were synthesized and structurally identified. While the direct addition of the doubly deprotonated bulky imidazolidinium chloride salts [Dipp,4-RNHC-H]Cl (with Dipp = 2,6-diisopropylphenyl, R = H (2-hydroxyphenyl), and R = Me (2-hydroxy-4-methyl-phenyl)) with chloro-titanium precursor favors the formation of single stereoisomer corresponding to the bis-ligated titanium complexes trans-([κ2-C,O]-Dipp,4-RNHC)2TiCl2 (R = H (2-hydroxyphenyl) for 4aH, and R = Me (2-hydroxy-4-methyl-phenyl) for 4aMe), the reactivity with sterically less hindered imidazolidinium chloride salts [Mes,HNHC-H]Cl and [Dep,HNHC-H]Cl as protio-ligands (with Mes = 2,4,6-trimethylphenyl and Dep = 2,6-diethylphenyl) did not lead to single stereoisomer, but rearranged into a tetradentate salophen-like complexes cis-([κ4-O,N,N,O]-bis(imidazolidinylidene)TiCl2 as major isomer via presumably the NHCs dimerization from bis-ligated intermediates. These results combined with topographic steric maps as well as the buried volume descriptor (%Vbur) indicate that bidentate bulky N-Dipp-substituted NHC ligands offer some level of steric protection preventing the formation of other possible bis-ligated (C,O)-NHC-titanium stereoisomers and constitutional isomers.

The effect of ligand symmetry on the ratiometric luminescence characteristics of lanthanides.

This work demonstrated that the ligand symmetry of europium(iii) complexes controls the ratiometric luminescence characteristics of lanthanides. Nona-coordinated europium(iii) complexes having unsymmetrical β-diketonate ligands (Cs) exhibit distinctive ratiometric spectral variations in the extremely narrow f-f transition bands over the temperature range from 253 to 323 K. In contrast, no such ratiometric change can be observed in a series of nona-coordinated europium(iii) complexes containing symmetrical β-diketonate ligands (C2v). The remarkable difference depending on the ligand symmetry (Csvs. C2v) suggests that the coordination rearrangement of β-diketonate in the complex causes ratiometric spectral variations in extremely narrow f-f transition bands, where two europium(iii) complex isomers exist in the solution equilibrium. A self-calibration method using dual iso-emissive points is reported, where self-calibration using the two emission intensities at the iso-emissive points reduces the coefficient of variation in luminescence thermometry.

Tetranuclear and dinuclear phenoxido bridged copper complexes based on unsymmetrical thiosemicarbazone ligands.

We report on the synthesis of new dinucleating phenol-based "end-off" compartmental ligands HLMeH and HLMe2 bearing two different binding sites, one bis(2-methylpyridyl)aminomethyl (BPA) and one thiosemicarbazone (TSC) site, and their corresponding copper(ii) complexes 1t and 2d. With the ligand HLMeH, a tetranuclear entity (1t) has been isolated in the solid state, whereas with HLMe2, which differs from HLMeH by a methyl substituent on the N-terminal amino group of the TSC arm, a dinuclear form (2d) is obtained. X-ray crystallography analysis shows that the nuclearity di vs. tetra is modulated by interactions between copper atoms and hydroxido bridges along with the sulphur atoms of TSC arms. From a magnetic point of view, 1t can be considered as an association of two dinuclear forms leading for both complexes to overall antiferromagnetic coupling. Analysis in acetonitrile solution of structure-property relationships has been carried out by comparing their UV/Vis, electrochemistry, ESI-MS, and NMR (variable temperature and DOSY = diffusion ordered spectroscopy) properties with trends from computational calculations (DFT). HRMAS-DOSY (High Resolution Magic Angle Spinning) NMR spectroscopy has been performed to evaluate the presence of different species in solution at room temperature.

Tri- and hexa-nuclear NiII-MnII complexes of a N2O2 donor unsymmetrical ligand: synthesis, structures, magnetic properties and catalytic oxidase activities.

A new mononuclear Ni(ii) complex, [NiL] (1) of an unsymmetrically dicondensed N2O2 donor ligand, H2L (where H2L = N-α-methylsalicylidene-N'-salicylidene-1,3-propanediamine), has been synthesized. Complex 1, on reaction with Mn(ii) in the presence of different co-anions, yielded three heterometallic NiII-MnII complexes, [(NiL)2Mn(NCS)2]·CH3CN (2), [(NiL)2Mn(N3)(H2O)](ClO4)·H2O (3) and [{(NiL)2Mn(H2O)}2(μ1,3-N3)](ClO4)3 (4). Single crystal structural analyses show that complexes 2 and 3 contain similar bent trinuclear NiII2MnII structures, with the difference that in complex 2 two SCN- ions and in 3, one N3- and one H2O molecule are coordinated to the Mn(ii) centre. Complex 4 possesses a hexanuclear structure, in which two trinuclear NiII2MnII units are connected via a single μ1,3-azido bridge. Variable temperature dc molar magnetic susceptibility measurements reveal that the two Mn(ii) centres in complex 4 are antiferromagnetically coupled with an exchange coupling constant (J) of -3.73 cm-1. Among the three heterometallic complexes, only 3 and 4 show bio-mimetic catalytic oxidase activities. For catecholase like activity, the turnover numbers (Kcat) of complexes 3 and 4 are 984 and 2081 h-1, respectively, whereas for phenoxazinone synthase-like activity, the turnover numbers of complexes 3 and 4 are 6351 and 10 545 h-1, respectively. The high catalytic oxidase activities of complexes 3 and 4 in contrast to the inactivity of complex 2 are attributed to the coordination of a water molecule to the Mn(ii) centre in the former structures, which facilitates the binding of the substrate with the catalyst. Mass spectral analyses suggest the probable formation of a complex-substrate intermediate in these catalytic reactions and cyclic voltammetry measurements show that Ni(ii) is reducible to Ni(i).

Synthesis, Characterization, and Catalytic Properties of Iridium Pincer Complexes Containing NH Linkers

A series of tert-butyl-substituted pincer ligands based on 1,3-diaminobenzene and 3-aminophenol scaffolds, tBu4PXCYP (1e, X = Y = NH; 1f, X = NH; Y = O) and the corresponding iridium hydridochloro complexes (tBu4PXCYP)IrHCl (2e, X = Y = NH; 2f, X = NH; Y = O) were prepared with moderate yields and high purity and were fully characterized by 1H and 31P NMR spectroscopy. Unsymmetrical hybrid pincer ligands R2PNCOPtBu2 (1g, R = isopropyl; 1h, R = cyclohexyl) were prepared conveniently in high yield via a one-pot procedure by judiciously choosing reaction conditions and base; the corresponding iridium hydrido chloro complexes iPr2PNCOPtBu2IrHCl (2g) and Cy2PNCOPtBu2IrHCl (2h) were synthesized by the reaction of [IrCl(COE)2]2 with ligands. X-ray crystallography reveals that these iridium pincer complexes adopt similar square-pyramidal geometries and exhibit strong intermolecular hydrogen bonding between the NH linker and chloride ions of the adjacent iridium complex in the solid state. 1H NMR chemical shifts o...

Phosphinomethylation of [1′-(diphenylphosphino)ferrocenyl]-methylamines as a route to unsymmetric ferrocene diphosphine ligands

[1′-(Diphenylphosphino)ferrocenyl]methylamine (1) reacts with Ph2PH/(CH2O)x or [Ph2P(CH2OH)2]Cl to give mixtures of Ph2PfcCH2NHCH2PPh2 and Ph2PfcCH2N(CH2PPh2)2 in which the triphosphine dominates (fc = ferrocene-1,1′-diyl). To avoid unwanted two-fold phosphinomethylation, the amine group in 1 was alkylated. As expected, the reaction of the N-methyl analogue Ph2PfcCH2NHMe (5), obtained by reductive methylation of the aldehyde Ph2PfcCHO, with [Ph2P(CH2OH)2]Cl, only led to the diphosphine Ph2PfcCH2N(Me)CH2PPh2 (6). The diphosphine was structurally characterized and further reacted with [PdCl2(MeCN)2] and [PdCl(Me)(cod)] (cod = η2:η2-cycloocta-1,5-diene), affording the respective trans-chelate complexes [PdCl(X){Ph2PfcCH2N(Me)CH2PPh2-κ2P,P′}] (7a: X = Cl; 7b: X = Me), which were also structurally authenticated by X-ray diffraction analysis.

Silver gelation-promoted solid-state [2+2] reaction of unsymmetrical olefin-containing ligand

Silver gelation-promoted solid-state [2+2] reaction of unsymmetrical olefin-containing ligand