Synthesis and characterization of some new Co(II) and Cd(II) macroacyclic Schiff-base complexes containing piperazine moiety

Three Cd(II) or Co(II) macroacyclic Schiff-base complexes [CoL¹Br]ClO₄ (1), [CdL²Cl]ClO₄ (2) and [CdL³(NO₃)]ClO₄ (3) were prepared by template condensation of 2-pyridinecarboxaldehyde and three different amines containing piperazine moiety, N,N′-bis(2-aminoethyl)piperazine, N,N′(2-aminoethyl)(3-aminopropyl)piperazine and N,N′-bis(3-aminopropyl)piperazine, in the presence of Co(II) or Cd(II) metal ions, respectively. All complexes have been studied with IR, FAB mass and microanalysis and for complex (3) by ¹H and ¹³C NMR spectra. One of these complexes, [CdL³(NO₃)]ClO₄ (3) has been characterized through X-ray crystallography. In complex (3), the Cd(II) ion is coordinated by the six nitrogen donor atoms from the ligand and by one oxygen atom from a monodentate nitrate ion in a N₆O environment.     

Metal or ammonium alginates as Lewis base catalysts for the 1,2-addition of silyl nucleophiles to carbonyl compounds

Several metal (Na⁺, Ca²⁺) or ammonium (n-Bu₄N⁺) derivatives of alginic acid, an abundant bio-polymer obtained from the cell walls of brown algae, were synthesized. Their potential to act as organocatalysts to catalyze the 1,2-addition of various silyl derivatives to carbonyl compounds was evaluated for the first time. Ammonium alginate 1h is able to promote the reaction in modest to good isolated yields (up to 98%) affording access to a large range of substrates (β-cyano alcohols or ester, β-substituted methylacrylate or acrylonitrile, and cyanohydrin) by using only 5 mol % of catalyst.     

Synthesis and characterization of metal complexes of N-alkyl-N-phenyl dithiocarbamates

Ammonium N-ethyl-N-phenyl dithiocarbamate (L¹) and N-butyl-N-phenyl dithiocarbamate (L²), and their group 12 metal complexes formulated as Zn₂L¹₄, CdL¹₂, HgL¹₂, Zn₂L²₄, CdL²₂, HgL²₂ have been synthesized and characterized by elemental analyses, IR, ¹H and ¹³C NMR spectroscopy. The crystal structures of the zinc complexes (Zn₂L¹₄ and Zn₂L²₄) are also reported. Single crystal analyses of the two complexes revealed the presence of distorted trigonal bipyramidal and tetrahedral coordination geometry about the metal ions. The dithiocarbamate acts as bidentate chelating and bidentate bridging ligands between the metal ions giving centrosymmetric dimeric molecules. The apparent substitution of the ethyl substituents in L¹ by the butyl groups in L² results in profound change in structure.     

A luminescence probe for measurements of electron-exchange rates in polymer films on electrodes

The effect of metal ions on the, reduction of 1,10-phenanthroline-5,6-quinone (1), 5,8-quinolinequinone (II) and 6,7-dichloro-5, 8-quinolinequinone (III) has been investigated in 50% dimethylsulfoxide+water solvent. 1 contains the 1,10-phenanthroline structure in both its quinone and hydroquinone forms, while II and III contain the 8-hydroxyquinoline structure in the hydroquinone forms. Complexation of the hydroquinones of II and III by metal ions causes positive shifts in the quinone half-wave potentials. These shifts have been used to calculate conditional formation constants for Pb²⁺(II) and Pb²⁺ and Zn²⁺(III). The quinone form of I binds strongly to Ni²⁺, Co²⁺ and Zn²⁺ but not to Ca²⁺. Mg²⁺. Mg₂₊. Mn²⁺ and Pb²⁺. With the latter four metals, binding to the hydroquinone from of I was detected and formation constants were determined. In addition to binding both the quinone and hydroquinone forms at the nitrogen atoms, Ni₂₊ Co²⁺ and Zn²⁺ formed complexes at the 1,2-dihydroxy site of the hydroquinone of I.     

2-Electron reduction of N2O yields a new ligand binding mode: N-Nitrosoimide

A new mode of bonding of the traditionally weak ligand N₂O to highly reducing transition metal complexes is described based on DFT calculations for a variety of late transition metals. These η¹-NNO can be singly bent (at the central nitrogen) or doubly bent (at both N), and thus involve a triple or double M/N bond, respectively. The ligand is therefore properly termed an N-nitrosoimide, N₂O²⁻.     

Syntheses and crystal structures of copper mixed-ligand complexes of multidentate enaminones and acetate anions

Reactions of ferrocenoylacetone with 2-(aminomethyl)pyridine and N-(2-hydroxyethyl)-1,2-diaminoethane afford the multidentate enaminones HL¹ and H₃L², respectively. Reactions of copper acetate with the two enaminones generate the corresponding mixed-ligand complexes I and II, which are formulated as [CuL¹(OAc)] and [Cu(H₂L²)(OAc)], respectively. The structures of HL¹, I and II have been determined by single-crystal X-ray crystallography. In complex I, HL¹ acts as a monoanionic tridentate donor via the carbonyl oxygen, deprotonated enamine nitrogen and pyridyl nitrogen atoms, the acetate anion is monodentate and the coordination geometry of the central metal is square planar. In complex II, H₃L² is a monoanionic tetradentate ligand via the carbonyl oxygen, deprotonated enamine nitrogen, secondary amine nitrogen and hydroxy oxygen atoms, the acetate anion is monodentate and the coordination geometry of the central metal is a distorted trigonal bipyramid.     

DNA binding and photocleavage specificities of a group of tricationic metalloporphyrins

The interactions of 5,10,15-tris(1-methylpyridinium-4-yl)-20-(4-hydroxyphenyl)porphyrinatozinc(II) Zn[TMPyHP]³⁺ (2) along with Cu[TMPyHP]³⁺ (3), Co[TMPyHP]⁴⁺ (4), Mn[TMPyHP]⁴⁺ (5) and the free base porphyrin H₂[TMPyHP]³⁺ (1) with duplex DNA have been studied by using a combination of absorption, fluorescence titration, surface-enhanced Raman spectroscopy (SERS), induced circular dichroism (ICD) spectroscopy, thermal DNA denaturation, viscosity measurements as well as gel electrophoresis experiment. Their binding modes and intrinsic binding constants (K_b) to calf DNA (CT DNA) were comparatively studied and were found significantly influenced by different metals coordinated with the porphyrin plane. Except 3, which has four-coordination structure at the metal, all the metal derivatives showed non-intercalative DNA-binding mode and lower K_b than the free base porphyrin 1, most probably due to the steric hindrance results from the axial ligands of the inserted metals which are five or six-coordination structures. Meanwhile, the insertion of metals into cationic porphyrin greatly removed the self-aggregation of the metal-free porphyrins, and thus fully enhanced the singlet oxygen (¹O₂) productivities in the DNA photocleavage experiments. Therefore, these metalloporphyrins have comparable DNA cleavage ability with the free base porphyrin.     

Study of complexes of platinum group metals containing nitrogen bases derived from pyridine aldehydes: Interesting molecular structures with unpredicted bonding modes of the ligands

A series of mono-cationic dinuclear half sandwich ruthenium, rhodium and iridium metal complexes have been synthesized using ((pyridin-2-yl)methylimino)nicotinamide (L1) and ((picolinamido)phenyl)picolinamide (L2) ligands: [(η⁶-arene)₂Ru₂(μ-L1)Cl₃]⁺ (arene = C₆H₆, 1; p-ⁱPrC₆H₄Me, 2; C₆Me₆, 3), [(η⁵-C₅Me₅)₂M₂(μ-L1)Cl₃]⁺ (M = Rh, 4; Ir, 5), and [(η⁶-arene)₂Ru₂(μ-L2)(μ-Cl)]⁺ (arene = C₆H₆, 6; p-ⁱPrC₆H₄Me, 7; C₆Me₆, 8), [(η⁵-C₅Me₅)₂M₂(μ-L2)Cl₂]⁺ (M = Rh, 9; Ir, 10). All the complexes have been isolated as their hexafluorophosphate salts and fully characterized by use of a combination of NMR and IR spectroscopy. The solid state structure of three representatives 4, 6 and 9 has been determined by X-ray crystallographic studies. Interestingly, in the molecular structure of 4, the first metal is bonded to two nitrogen atoms whereas the second metal center is coordinated to only one nitrogen atom with two terminal chloride ligands. Fascinatingly in the case of the complexes with the symmetrical ligand L2, both ruthenium centers having η⁶-arene groups are bonded to nitrogen atoms with a bridging chloride atom between the two metal centers, whereas the metals with η⁵-Cp∗ groups are bonded to the ligand N,O and N,N fashion.     

Catalytic efficacy of Schiff-base copper(II) complexes: Synthesis,X-ray structure and olefin oxidation

Three copper(II) Schiff-base complexes, [Cu(L¹)(H₂O)](ClO₄) (1), [Cu(L²)] (2) and [Cu(L³)] (3) have been synthesized and characterized [where HL¹ = 1-(N-ortho-hydroxy-acetophenimine)-2-methyl-pyridine], H₂L² = N,N′-(2-hydroxy-propane-1,3-diyl)-bis-salicylideneimine and H₂L³ = N,N′-(2,2-dimethyl-propane-1,3-diyl)-bis-salicylideneimine]. The structure of complex 1 has been determined by single crystal X-ray diffraction analysis. In complex 1, the copper(II) ion is coordinated to one oxygen atom and two nitrogen atoms of the tridentate Schiff-base ligand, HL¹. The fourth coordination site of the central metal ion is occupied by the oxygen atom from a water molecule. All the complexes exhibit high catalytic activity in the oxidation reactions of a variety of olefins with tert-butyl-hydroperoxide in acetonitrile. The catalytic efficacy of the copper(II) complexes towards olefin oxidation reactions has been studied in different solvent media.     

Can Cyclen Bind Alkali Metal Azides? A DFT Study as a Precursor to Synthesis

Can cyclen (1,4,7,10‐tetraazacyclododecane) bind alkali metal azides? This question is addressed by studying the geometric and electronic structures of the alkali metal azide‐cyclen [M(cyclen)N₃] complexes using density functional theory (DFT). The effects of adding a second cyclen ring to form the sandwich alkali metal azide‐cyclen [M(cyclen)₂N₃] complexes are also investigated. N₃^? is found to bind to a M⁺(cyclen) template to give both end‐on and side‐on structures. In the end‐on structures, the terminal nitrogen atom of the azide group (N1) bonds to the metal as well as to a hydrogen atom of the cyclen ring through a hydrogen bond in an end‐on configuration to the cyclen ring. In the side‐on structures, the N₃ unit is bonded (in a side‐on configuration to the cyclen ring) to the metal through the terminal nitrogen atom of the azide group (N1), and through the other terminal nitrogen atom (N3) of the azide group by a hydrogen bond to a hydrogen atom of the cyclen ring. For all the alkali metals, the N₃‐side‐on structure is lowest in energy. Addition of a second cyclen unit to [M(cyclen)N₃] to form the sandwich compounds [M(cyclen)₂N₃] causes the bond strength between the metal and the N₃ unit to decrease. It is hoped that this computational study will be a precursor to the synthesis and experimental study of these new macrocyclic compounds; structural parameters and infrared spectra were computed, which will assist future experimental work.     

Coordination behaviour in transition metal complexes of asymmetric NPN ligands

Two bicyclic, chiral aminophosphine ligands, namely 4R, 9R-1,3-bis(pyridin-2-ylmethyl)-2-(2-propyl)octahydro-1H-1,3,2-benzodiazaphosphole (1) and 4R, 9R-1,3-bis(pyridin-2-ylmethyl)-2-(2-ethoxy)octahydro-1H-1,3,2-benzodiazaphosphole (2) have been prepared from 1R, 2R-diaminocyclohexane and the appropriate dichlorophosphine and the nature of their coordination to a number of transition metals explored. Ligand 1 coordinates to Pd(II) and Pt(II) as a terdentate donor to give complexes of the type [M(κ³-N,P,N-1)Cl]⁺ whereas ligand 2 favours bidentate κ²-P,N coordination to give the complexes M(κ²-P,N-2)Cl₂. The study of the coordination chemistry of the NPN ligand 1 is frustrated by its ready decomposition to an unknown species which appears to be promoted by transition metals. The ligand 2 does not undergo such a transformation and its metal chemistry is more readily examined. Aside from the Pt(II) and Pd(II) complexes above, 2 has been coordinated to Cr(0) and Mo(0) in the octahedral complexes M(κ²-P,N-2)(CO)₄ and Au(I) in linear Au(κ¹-P-2)Cl. All the complexes have been fully characterised by spectroscopic and analytical techniques including a single-crystal X-ray structure analysis of [Pt(κ³-N,P,N-1)Cl]Cl, 3.     

Efficient enantiorecognition of ruthenium(II) complexes by silica-bound teicoplanin

A series of chiral tris-diimine ruthenium(II) complexes have been resolved by HPLC on a chiral stationary phase. The stationary phase (CSP1) was prepared by covalent attachment of the glycopeptide antibiotic teicoplanin to isocyanate activated silica gel. CSP1 selectively retains the enantiomers of [Ru(L)₃]²⁺ (L=2,2′-bypyridine (bpy), 1,10-phenanthroline and 4,7-diphenyl-1,10-phenanthroline), with a preference for the Δ isomer. For the mixed-ligand complexes [Ru(bpy)₂pztr]⁺ and [Ru(bpy)₂pytr]⁺ (Hpztr=3-(pyrazin-2-yl)-1,2,4-triazole, Hpytr=3-(pyridin-2-yl)-1,2,4-triazole), where the triazole unit is bound to the metal centre either through the N² or the N⁴ nitrogen of the ring, CSP1 discriminates both the enantiomers and the regioisomers. Diastereo- and enantioselective association was also observed between CSP1 and the stereoisomers of the dinuclear complex ((Ru(bpy)₂)₂bpt]³⁺ (Hbpt=3,5-bis(pyridin-2-yl)-1,2,4-triazole), with differences in binding affinities of 1.4 kJ/mol between the homochiral enantiomers.     

Methylene Bridged P(III) and P (V) Phosphiniminato-Phosphanes: Versatile Ligands And Substituents for Metals and Metalloids

Abstract

Recent studies¹ have shown that the mono oxidized phosphanolminatophosphane Me₃SiN=PPh₂CH₂PPh₂ 1 is a versatile ligand for a variety of transition metals in high and low oxidation states. This heterodifunctional ligand may bind to metals via the “hard” (N) or the “soft”(P(III)) centres; the former favours high oxidation states and “early” transition metals, the latter, low oxidation states and “late” transition metals. Monodentate or bidentate complexation is observed and in the latter case chelation or bridging is possible. Elimination of Me₃SiCl from a metal halide or migration of Me₃Si group to a terminal oxygen atom leads to metal nitrogen sigma bond formation. To modify the basicity at nitrogen a variety of approaches have been employed. Metathetical elimination of Me₃SiX from activated halogenated aromatics leads to functionalisation at N. The R₃Sn and R₃Ge analogs of 1 have also been made by extensions of the Staudinger reaction. Reactions of 1 and its N-aromatic, N-Ge, and N-Sn analogs with a variety of metals wiil be described. In water, 1 produces the unstable parent imine which has been trapped as a coordination complex of Pd(II) and Pt(II) metals. The reactions of halides produces a variety of N substituted compounds of non metals (eg; =N-SePh) and metals (eg; =N-TiR₃) which demonstrate the important heterodifunctional character of the ligand system.     

Feasibility of improvement in analytical performance in laser ablation inductively coupled plasma-mass spectrometry (LA-ICP-MS) by addition of nitrogen to the argon plasma

Addition of nitrogen to an argon ICP in LA-ICP-MS has been found to increase sensitivity and consequently reduce oxide to metal ratios (MO⁺/M⁺) for the reference elements Ce and Th. Addition of about 1% v/v N₂ to the coolant flow increased sensitivity, reducing MO⁺/M⁺ ratios from about 0.6% to about 0.2%. Addition of about 12% N₂ to the cell flow had a similar effect, being greatest at a higher forward rf plasma power (1700 W). The increased sensitivity may be useful in practical analyses; N₂ consumption is very small.     

Synthesis and structural characterization of nickel(II), copper(II) and zinc(II) complexes with the hexadentate ligand 2,13-bis(2-pyridylmethyl)-3,14-dimethyl-2,6,13,17-tetraazatricyclo[14,4,01.18,07.12]docosane

The complexes [Ni(L²)]Cl₂·10H₂O (1), [Cu(L²)](ClO₄)₂·3H₂O (2), [Cu₂(L²)(H₂O)₂Cl₂]Cl₂ (3) and [Zn(L²)]Cl₂·10H₂O (4) (L²=2,13-bis(2-pyridylmethyl)-3,14-dimethyl-2,6,13,17-tetraazatricyclo[14,4,0^1.18,0^7.12]docosane) have been synthesized and characterized by X-ray crystallography, electronic absorption, ¹³C NMR and magnetic susceptiblity as well as cyclic voltammetry. The crystal structures of 1 and 4 show that the metal ion has a slightly distorted octahedral geometry with two nitrogen atoms of the pendant arms at the axial positions. However, 2 exhibits a square-planar geometry, coordinated by secondary and tertiary nitrogen donors of the macrocycle. Furthermore, 3 reveals a binuclear structure and a center of symmetry in which the each copper ion is coordinated by a distorted square-pyramidal geometry with an N₃Cl basal plane and a water molecule in the apical position. The magnetic behavior for 3 shows that a ferromagnetic interaction between the copper(II) ions is predominant at intermediate temperature and then a weaker antiferromagnetic coupling is involved at lower temperature. Cyclic voltammetric studies for 1–3 indicate that 1 undergoes quasi-reversible one-electron oxidation to the Ni(III) and reversible one-electron reduction to the Ni(I), 2 undergoes a irreversible one-electron reduction to the Cu(I) state, while 3 undergoes an overall quasi-reversible two-electron reduction to the binuclear Cu(I) complex.     

Coordination compounds of disulphur dinitride

Summary Coordination compounds of the S₂N₂ molecule including methods for their preparation, reactivities, i.r. data, structures, and aspects of chemical bonding are reviewed. Methods of synthesis include reactions of S₂N₂, S₄N₄ or (NSCl)₃ with metal halides, metal complexes such as carbonyls, or even metals themselves. In all cases, the planar S₂N₂ ring is coordinated, usuallyvia both, of its nitrogen atoms so that S₂N₂ acts as a bridging ligand between two metal centres; short contact distances imply that halogen atoms linked to the metal atoms show some interaction with the sulphur atoms. The stability of S₂N₂ is greatly enhanced by coordination. In the i.r. spectra, two characteristic S₂N₂ vibrations assist identification of the S₂N₂ species, a ring stretching mode being observable atca. 850 cm^–1 and the out-of-plane deformation at 450–490 cm^–1.     

Liquid–liquid extraction of palladium(II) and gold(III) with N-benzoyl-N′,N′-diethylthiourea and the synthesis of a palladium benzoylthiourea complex

N-Benzoylthioureas have been reported to form complexes with gold (III) and palladium (II) and other transition metals. In this study, an N-benzoyl-N′,N′-diethylthiourea (3f) ligand was used in the solvent extraction of palladium(II) and gold(III) from aqueous chloride media (0.1 mol l−1 NaCl). The distribution coefficient was determined as a function of both metal concentration in the aqueous phase and extractant concentration in the organic phase. The experimental distribution data were numerically analysed by letagrop-distr software in order to obtain the thermodynamic model corresponding to the metal extraction. It is found that pH does not affect the metal extraction process in the 1–2 pH range. Synthesis of the palladium benzoyl thiourea complexes was carried out by mixing quantities of metal and ligand solutions in methanol in a 1:2 ratio stoichiometric. Yields of 74 and 80.9% were obtained for the Pd-3c and Pd-3f complexes. In order to confirm the formation of the palladium complexes, NMR, FTIR and MS analyses were performed. From MS analyses a complex stoichiometry 1:2 (metal:ligand) was confirmed. The formation of crystals of palladium N-benzoyl-N′,N′-diethylthiourea complex (Pd-3f) in the methanolic solution allows the characterisation of the complex structure by XRD. The resulting structure is described and discussed. Bis(1,1,-diheptadecyl-3-benzoyl-thioureate)palladium(II) (Pd-3c) and bis(1,1,-diheptadecyl-3-benzoyl-thioureate)palladium(II) (Pd-3f) were used as ionophores in polymeric membrane electrodes. Their potentiometric responses to different anionic metal chlorocomplexes are evaluated and discussed taking into consideration the results obtained in the liquid–liquid distribution studies. A nernstian response was only obtained for AuCl4 − (PDL=8.8×10−8) and PdCl4 2− (PDL=1.5×10−4 M) with a selectivity coefficient of KAuCl4-, PdCl42−pot=−3.4, calculated taking AuCl4 − as being the primary anion.     

Synthesis,structure, photophysical properties and biological activity of a cobalt(II) coordination complex with 4,4′-bipyridine and porphyrin chelating ligands

A new bioactive material of cobalt(II) with 5,10,15,20-tetrakis[4 (benzoyloxy)phenyl] porphyrin (TPBP) and bpy ligands ([Co^II(TPBP)(bpy)₂] 1) has been synthesized and characterized by Single-crystal X-ray diffraction (SCXRD), spectroscopic methods and quantum-chemistry calculations. In the crystalline structures of six coordinated Co(II) [Co^II(TPBP)(bpy)₂] 1, linear 1D polymeric chains were observed in which all the porphyrin units are aligned parallel to each other. The crystal packing is stabilized by inter-and intramolecular C–H⋯O and C–H⋯N hydrogen bonds, and by weak C–H⋯Cg π interactions. Interestingly, NBO–Second-order perturbation theory analysis, carried out at the UB3LYP/6-31G(d)/SDD DFT level of theory, demonstrated that a two-center bond between the nitrogen atoms and the cobalt ions (Co) was not found, the Co–N_py/bp interactions are coming from an electronic delocalization between the N_py/N_bp filled orbitals to the anti-bonding LP*(4) and LP*(5) metal NBOs. Mass spectroscopy, and elemental analysis were also investigated to confirm the molecular structure. The downfield shift and the peak broadening of the axial ligand resonances observed in the ¹H NMR indicated the contiguity to the paramagnetic Co(II) center. Additionally, the photophysical properties have been evaluated by UV–visible absorption, and fluorescence emission spectroscopies. Finally, bioactivity investigations revealed that free porphyrin TPBP, Co^IITPBP and complex 1 could be used as potential antioxidant agents.     

Coordination chemistry of neutral quinolyl- and aminophenylcyclopentadiene derivatives

The cyclopentadiene and indene derivatives 1–4 being functionalised by a dimethylaniline and quinolyl group, respectively, were treated with metal carbonyl complexes. Whereas cyclopentadienes (C₅R₅H) normally loose one hydrogen atom prior or during metal complex formation, leading to negatively charged cyclopentadienide ligands, the compounds 1–4 are able to act as neutral ligands without hydrogen loss. Consequently transition metal complexes with coordination of the nitrogen donor and a CC double bond of the five membered ring have been obtained. In some cases a hydrogen atom is eliminated and the expected η⁵-(C₅R₅) complexes are formed. Reaction of Ru₃(CO)₁₂ with 2 leads to the binuclear η⁶-fulvene complex 8. The octahedral molybdenum complex 9 and the square planar rhodium(I) complexes 10 and 11 which were obtained from Mo(CO)₆ and [Rh(CO)₂Cl]₂, respectively, are rare examples of η²-(C₅R₅H) coordination to metal atoms.     

Ruthenium monoterpyridine complexes with 2,6-bis(benzoxazol-2-yl)pyridine as an ancillary ligand: Synthesis,structure and spectral studies

Ruthenium monoterpyridine complexes, [1]⁺ and [2]²⁺, with 2,6-bis(benzoxazol-2-yl)pyridine as an ancillary ligand, L, have been synthesized and characterized by UV–Vis, FT-IR and ¹H NMR spectroscopic techniques. The formulations of the complexes were confirmed by the single crystal structure of their perchlorate salts. In both complexes, the Ru^II center is hexa-coordinated in a distorted geometry. In complex [1]⁺, the ancillary ligand L behaves as a bidentate ligand; in [2]²⁺, however, it binds the metal center as a tridentate ligand. The central pyridine nitrogen of terpyridine (N_p,trpy) is in a cis position with respect to the central pyridine nitrogen of the ancillary ligand (N_p,benz) in complex [1]⁺ and in a trans-position in complex [2]²⁺. The cis orientation of N_p,trpy and N_p,benz in complex [1]⁺ forces L to behave as bidentate. The quasi-reversible Ru^II/Ru^III couple appears at 0.90 and 1.44 V versus SCE in the case of complex [1]⁺ and [2]²⁺, respectively. [1]⁺, in the presence of aqueous AgNO₃, affords [2]²⁺ through an intramolecular dissociative interchange pathway.