Synthesis and characterisation of palladium(II) and platinum(II) compounds containing pyrazole-derived ligands: crystal structure of [PdCl2(HL)] (HL = 3-phenyl-5-(2-pyridyl)pyrazole)

Reaction of the ligands 3-phenyl-5-(2-pyridyl)pyrazole (HL¹), 3,5-bis(2-pyridyl)pyrazole (HL²), 3-methyl-5-(2-pyridyl)pyrazole (HL³) and 3-methyl-5-phenylpyrazole (HL⁴) with [MCl₂(CH₃CN)₂] (M = Pd(II), Pt(II)) or [PdCl₂(cod)] gives complexes with stoichiometry [PdCl₂(HL)₂] (HL = HL¹, HL², HL³), [Pt(L)₂] (L = L¹, L², L³) and [MCl₂(HL⁴)₂] (M = Pd(II), Pt(II)). The new complexes were characterised by elemental analyses, conductivity measurements, infrared and ¹H NMR spectroscopies. The crystal and molecular structure of [PdCl₂(HL¹)] was resolved by X-ray diffraction, and consists of monomeric cis-[PdCl₂(HL¹)] molecules. The palladium centre has a typical square planar geometry, with a slight tetrahedral distortion. The tetra-coordinated metal atom is bonded to one pyridine nitrogen, one pyrazolic nitrogen and two chloro ligands in a cis disposition. The ligand HL¹ is not completely planar.     

Exploring the coordination chemistry and reactivity of hemilabile N-alkylaminopyrazole ligands towards Pd(II)

Reaction of the N-alkylaminopyrazole (NN′N) ligands bis[(3,5-dimethyl-1-pyrazolyl)methyl]ethylamine (bdmae) and bis[(3,5-dimethyl-1-pyrazolyl)methyl]isopropylamine (bdmai) with [PdCl₂(CH₃CN)₂] in a 1:1 M/L ratio in CH₂Cl₂ produces cis-[PdCl₂(NN′N)] (NN′N = bdmae (1), bdmai (2)). The solid state structure of complex 1 was determined by X-ray diffraction studies. The bdmae ligand is coordinated through the two N_pz atoms to the metal atom, which completes its coordination with two chlorine atoms in a cis disposition.Treatment of the corresponding ligand with [PdCl₂(CH₃CN)₂] in 1:1 M/L ratio in the presence of AgBF₄ and metathesis with NaBPh₄ in CH₂Cl₂/CH₃OH (3:1) gave [PdCl(bdmae)](BPh₄) (3), and in the presence of NaBPh₄ in CH₂Cl₂/CH₃CN (3:1) gave [PdCl(bdmai)](BPh₄) (4). Complexes 1 and 2 were again obtained when complexes 3 and 4 were heated under reflux in a solution of Et₄NCl in acetonitrile. These Pd(II) compounds were characterised by elemental analyses, conductivity measurements, IR, ¹H and ¹³C{¹H} NMR, HMQC and NOESY spectroscopies. The NMR studies of the complexes prove the rigid conformation of the ligands when they are complexed.     

Synthesis, spectroscopic, thermal and X-ray structure characterization of 1,3-propanediammonium tetrathiomolybdate and N,N,N′,N′-tetramethylethylenediammonium tetrathiomolybdate

The title compounds 1,3-propanediammonium tetrathiomolybdate, (1,3-pnH₂)[MoS₄], 1 and, N,N,N′,N′-tetramethylethylenediammonium tetrathiomolybdate, (tmenH₂)[MoS₄], 2, were prepared by reacting the ammonium salt of [MoS₄]²⁻ with the corresponding organic diamine. In 1 and 2 the organic diamines 1,3-propanediamine (1,3-pn) and N,N,N′,N′-tetramethylethylenediamine (tmen) are present in their diprotonated form. The reaction of 1 or 2 with [Ni(en)₃]Cl₂ · 2H₂O (en is ethylenediamine) results in the formation of the highly insoluble complex tris(ethylenediamine)Ni(II) tetrathiomolybdate, [Ni(en)₃][MoS₄], in quantitative yields. 1 and 2 have been characterized by chemical analysis, vibrational, UV-Vis and NMR spectroscopy, TG-DTA-MS and single crystal X-ray crystallography. Compound 1 is thermally more stable compared to 2. Both complexes decompose in a single step forming amorphous molybdenum sulfide. The structure of the title complexes can be described as consisting of tetrahedral [MoS₄]²⁻ dianions which accept a complex series of H-bonds from the organic dications. The strength and number of these hydrogen bonds affect the Mo-S bond lengths.     

Synthesis and structure of dichloropalladium(II) complexes of heteroleptic N,S- and N,Se-donor ligands based on the 2-organochalcogenomethylpyridine motif, and Mizoroki-Heck catalysis mediated by complexes of N,S-donor ligands

Ligands containing the 2-organochalcogenomethylpyridine motif with substituents in the 4- or 6-position of the pyridyl ring, R⁴,R⁶-pyCH₂ER¹ [R⁴ = R⁶ = H, ER¹ = SMe (1), SeMe (2), SPh (6), SePh (7); R⁴ = Me, R⁶ = H, ER¹ = SMe (3), SPh (8), SePh (9); R⁴ = H, R⁶ = Me, ER¹ = SMe (4), SPh (10), SePh (11); R⁴ = H, R⁶ = Ph, ER¹ = SMe (5), SPh (12), SePh (13)] are obtained on the reaction of R⁴,R⁶-pyMe with LiBuⁿ followed by R¹EER¹. On reaction with PdCl₂(NCMe)₂, the ligands with a 6-phenyl substituent form cyclopalladated species PdCl{6-(o-C₆H₄)pyCH₂ER¹-C,N,E} (5a, 12a, 13a) with the structure of 13a (ER¹ = SePh) confirmed by X-ray crystallography; other ligands form complexes of stoichiometry PdCl₂(R⁴,R⁶-pyCH₂ER¹). Complexes with R⁶ = H are monomeric with N,E-bidentate configurations, confirmed by structural analysis for 3a (R⁴ = Me, ER¹ = SMe), 7a (R⁴ = H, ER¹ = SePh) and 9a (R⁴ = Me, ER¹ = SePh). Two of the 6-methyl substituted complexes examined by X-ray crystallography are oligomeric with trans-PdCl₂(N,E) motifs and bridging ligands, trimeric [PdCl₂(μ-6-MepyCH₂SPh-N,S)]₃ (10a) and dimeric [PdCl₂(μ-6-MepyCH₂SePh-N,Se)]₂ (11a). This behaviour is attributed to avoidance of the Me···Cl interaction that would occur in the cis-bidentate configuration if the pyridyl plane had the same orientation with respect to the coordination plane as observed for 3a, 7a and 9a [dihedral angles 8.0(2)-16.8(2)°]. When examined as precatalysts for the Mizoroki-Heck reaction of n-butyl acrylate with aryl halides in N,N-dimethylacetamide at 120 °C, the complexes exhibit the anticipated trends in yield (ArI > ArBr > ArCl, higher yield for electron withdrawing substituents in 4-RC₆H₄Br and 4-RC₆H₄Cl). The most active precatalysts are PdCl₂(R⁴-pyCH₂SMe-N,S) (R = H (1a), Me (3a)); complexes of the selenium containing ligands exhibit very low activity. For closely related ligands, the changes SMe to SPh, 6-H to 6-Me, and 6-H to 6-Ph lead to lower activity, consistent with involvement of both the pyridyl and chalcogen donors in reactions involving aryl bromides. The precatalyst PdCl₂(pyCH₂SMe-N,S) (1a) exhibits higher activity for the reaction of aryl chlorides in Buⁿ₄NCl at 120 °C as a solvent under non-aqueous ionic liquid (NAIL) conditions.     

Synthesis, characterization, and magnetic properties of new homotrinuclear bis(oxamato) copper(II) complexes with an asymmetric central N,N′-bridge

The new mononuclear bis(oxamato) complex [n-Bu₄N]₂[Cu(obbo)] (1) (obbo=o-benzyl-bis(oxamato)) has been synthesized as a precursor for trinuclear oxamato-bridged transition metal complexes. Starting from 1 the homotrinuclear complexes [Cu₃(obbo)(pmdta)₂(NO₃)](NO₃)·CH₂Cl₂·H₂O (2) and [Cu₃(obbo)(tmeda)₂(NO₃)₂(dmf)] (3) have been prepared, where pmdta = N,N,N′,N″,N″-pentamethyldiethylenetriamine, tmeda = N,N,N′,N′-tetramethylethylenediamine and dmf = dimethylformamide. The crystal structures of 1-3 were solved. The magnetic properties of 2 and 3 were studied by susceptibility measurements versus temperature. For the intramolecular J parameter values of −111 cm⁻¹ (2) and −363 cm⁻¹ (3) were obtained.     

Pd(II) complexes containing N-alkyl-3-pyridine-5-trifluoromethyl pyrazole ligands: Synthesis, NMR studies and X-ray crystal structures

Palladium [PdCl₂(L)] complexes with N-alkylpyridylpyrazole derived ligands [2-(5-trifluoromethyl-1H-pyrazol-3-yl)pyridine (L¹), 2-(1-ethyl-5-trifluoromethyl-1H-pyrazol-3-yl)pyridine (L²), 2-(1-octyl-5-trifluoromethyl-1H-pyrazol-3-yl)pyridine (L³), and 2-(3-pyridin-2-yl-5-trifluoromethyl-pyrazol-1-yl)ethanol (L⁴) were synthesised. The crystal and molecular structures of [PdCl₂(L)] (L = L², L³, L⁴) were resolved by X-ray diffraction, and consist of monomeric cis-[PdCl₂(L)] molecules. The palladium centre has a typical square-planar geometry, with a slight tetrahedral distortion. The tetra-coordinate metal atom is bonded to one pyridinic nitrogen, one pyrazolic nitrogen and two chlorine ligands in cis disposition. Reaction of L (L², L⁴) with [Pd(CH₃CN)₄](BF₄)₂, in the ratio 1M:2L, gave complexes [Pd(L)]₂(BF₄)₂. Treatment of [PdCl₂(L)] (L = L², L⁴) with NaBF₄ and pyridine (py) and treatment of the same complexes with AgBF₄ and triphenylphosphine (PPh₃) yielded [Pd(L)(py)₂](BF₄)₂ and [Pd(L)(PPh₃)₂](BF₄)₂ complexes, respectively. Finally, reaction of [PdCl₂(L⁴)] with 1 equiv of AgBF₄ yields [PdCl(L⁴)](BF₄).     

Synthesis, structure, cytotoxic activities and DNA-binding properties of tetracopper(II) complexes with dissymmetrical N,N′-bis(substituted)oxamides as ligands

To compare the cytotoxicities and the DNA-binding properties in tetranuclear complexes with different bridging ligands, two tetracopper(II) complexes with formulae of [Cu₄(oxbe)₂Cl₂(bpy)₂]·4H₂O (1) and [Cu₄(oxbm)₂Cl₂(bpy)₂]·2H₂O (2) were synthesized, where H₃oxbe and H₃oxbm stand for N-benzoato-N′-(2-aminoethyl)oxamide and N-benzoato-N′-(1,2-propanediamine)oxamide, respectively, and bpy is 2,2′-bipyridine. Complex 1 was characterized by elemental analyses, IR and electronic spectra and single-crystal X-ray diffraction. The crystal structure reveals the presence of the circular tetranuclear copper(II) cations which are assembled by a pair of cis-oxamido-bridged dinuclear copper(II) units through carboxyl bridges. The crystal structure of complex 2 has been reported in our previous paper. However, the bioactivities were not studied. Cytotoxicities experiments reveal that both the two complexes exhibit cytotoxic effects against human hepatocellular carcinoma cell SMMC-7721 and human lung adenocarcinoma cell A549, and complex 1 has the better activities than those of complex 2. The results of the interactions between the two complexes and herring sperm DNA (HS-DNA) suggest that the two complexes interact with HS-DNA in the mode of intercalation with the intrinsic binding constants of 3.93 × 10⁴ M⁻¹ (1) and 2.48 × 10⁴ M⁻¹ (2). These results indicated that the bridging ligands may play an important role in the cytotoxicities and the DNA-binding properties of tetranuclear complexes.     

Aromatic N-oxide bridged copper(II) coordination polymers: Synthesis, characterization and magnetic properties

The complexes [Cu₂(o-NO₂-C₆H₄COO)₄(PNO)₂] (1), [Cu₂(C₆H₅COO)₄(2,2′-BPNO)]_n (2), [Cu₂(C₆H₅COO)₄(4,4′-BPNO)]_n (3), [Cu(p-OH-C₆H₄COO)₂(4,4′-BPNO)₂·H₂O]_n (4), (where PNO = pyridine N-oxide, 2,2′-BPNO = 2,2′-bipyridyl-N,N′-dioxide, 4,4′-BPNO = 4,4′-bipyridyl-N,N′-dioxide) are prepared and characterized and their magnetic properties are studied as a function of temperature. Complex 1 is a discrete dinuclear complex while complexes 2-4 are polymeric of which 2 and 3 have paddle wheel repeating units. Magnetic susceptibility measurements from polycrystalline samples of 1-4 revealed strong antiferromagnetic interactions within the {Cu₂}⁴⁺ paddle wheel units and no discernible interactions between the units. The complex 5, [Cu(NicoNO)₂·2H₂O]_n·4nH₂O, in which the bridging ligand to the adjacent copper(II) ions is nicotinate N-oxide (NicoNO) the transmitted interaction is very weakly antiferromagnetic.     

Reaction of [MCl2(CH3CN)2] (M = Pd(II), Pt(II)) compounds with N1-alkylpyridylpyrazole-derived ligands

Palladium(II) and platinum(II) complexes with N-alkylpyridylpyrazole-derived ligands, 2-(1-ethyl-5-phenyl-1H-pyrazol-3-yl)pyridine (L¹) and 2-(1-octyl-5-phenyl-1H-pyrazol-3-yl)pyridine (L²), cis-[MCl₂(L)] (M = Pd(II), Pt(II)), have been synthesised. Treatment of [PdCl₂(L)] (L = L¹, L²) with excess of ligand (L¹, L²), pyridine (py) or triphenylphosphine (PPh₃) in the presence of AgBF₄ and NaBPh₄ produced the following complexes: [Pd(L)₂](BPh₄)₂, [Pd(L)(py)₂](BPh₄)₂ and [Pd(L)(PPh₃)₂](BPh₄)₂. All complexes have been characterised by elemental analyses, conductivity, IR and NMR spectroscopies. The crystal structures of cis-[PdCl₂(L²)] (2) and cis-[PtCl₂(L¹)] (3) were determined by a single crystal X-ray diffraction method. In both complexes, the metal atom is coordinated by one pyrazole nitrogen, one pyridine nitrogen and two chlorine atoms in a distorted square-planar geometry. In complex 3, π-π stacking between pairs of molecules is observed.     

N,N′-Bis(3-methoxysalicylidene)propane-1,2-diamine mononuclear 4f and heterodinuclear Cu-4f complexes: Synthesis, crystal structure and electrochemical properties

Reactions of H₂L [H₂L = N,N′-bis(3-methoxysalicylidene)propane-1,2-diamine] and Ln(NO₃)₃ · 6H₂O give rise to two different mononuclear 4f complexes, namely, {[(H₂L)La(NO₃)₃(MeOH)] · H₂O}_n (1) and [(H₂L)Nd(NO₃)₃] (2). Further additions of Cu(Ac)₂ · H₂O to the mononuclear 4f complexes yield expected heterodinuclear Cu-4f complexes [LCu(Me₂CO)Ln(NO₃)₃] (3, Ln = Nd; 4, Ln = Eu; 5, Ln = Dy). Complex 1 is a unique 1D polymeric chain structure, and 2 is one of the few structurally characterized discrete hexadentate salen-type mononuclear 4f complexes. Complexes 3-5 are similar to their analogues. However, they are prepared by a reversed synthetic route in contrast to their isomorphic complexes. Electrochemical behavior of heterodinuclear Cu-4f complexes 3-5 has been examined by cyclic voltammetry in acetonitrile. The redox potential of heterodinuclear Cu-4f complexes 3-5 shows significant anodic shift comparing to that of mononuclear copper complex (LCu). A tendency of anodic shift was observed in a sequence of 3 < 4 < 5. This results from the modulating effect of coordination geometry around Cu(II) ion on redox potential.     

Synthesis of new palladium(II) compounds with several bidentate nitrogen-donor ligands: Structural analyses by H and C{H} NMR spectroscopy and crystal structures

The reaction of [PdCl₂(CH₃CN)₂] with N-alkylaminopyrazole (NN′) ligands, 1-[2-(ethylamino)ethyl]-3,5-dimethylpyrazole (deae), 1-[2-(ⁱpropylamino)ethyl]-3,5-dimethylpyrazole (deai), and 1-[2-(^tbutylamino)ethyl]-3,5-dimethylpyrazole (deat), affords a series of square planar Pd(II) complexes [PdCl₂(NN′)] (NN′ = deae (1), deai (2) and deat (3)). The solid-state structures of complexes 1 and 3 were determined by single crystal X-ray diffraction studies. The NN′ ligands are coordinated through the N_pz and N_amine atoms to the metal atom, which completes its coordination with two chlorine atoms in a cis disposition. These palladium(II) compounds were characterised by elemental analyses, conductivity measurements, IR, ¹H and ¹³C{¹H} NMR spectroscopies. The NMR studies of the complexes prove the rigid conformation of the ligands when they are complexed.     

Interaction of Pt(II) and Pd(II) complexes of terpyridine with 1-methylazoles: A combined experimental and density functional study

The synthesis and characterization of several complexes of the composition [{M(terpy)}_n(L)](ClO₄)_m (M = Pt, Pd; L = 1-methylimidazole, 1-methyltetrazole, 1-methyltetrazolate; terpy = 2,2′:6′,2″-terpyridine; n = 1, 2; m = 1, 2, 3) is reported and their applicability in terms of a metal-mediated base pair investigated. Reaction of [M(terpy)(H₂O)]²⁺ with 1-methylimidazole leads to [M(terpy)(1-methylimidazole)](ClO₄)₂ (1: M = Pt; 2: M = Pd). The analogous reaction of [Pt(terpy)(H₂O)]²⁺ with 1-methyltetrazole leads to the organometallic compound [Pt(terpy)(1-methyltetrazolate)]ClO₄ (3) in which the aromatic tetrazole proton has been substituted by the platinum moiety. For both platinum(II) and palladium(II), doubly metalated complexes [{M(terpy)}₂(1-methyltetrazolate)](ClO₄)₃ (4: M = Pt; 5: M = Pd) can also be obtained depending on the reaction conditions. In the latter two compounds, the [M(terpy)]²⁺ moieties are coordinated via C5 and N4. X-ray crystal structures of 1, 2, and 3 are reported. In addition, DFT calculations have been carried out to determine the energy difference between fully planar [Pd(mterpy)(L)]²⁺ complexes Ip-IVp (mterpy = 4′-methyl-2,2′:6′,2″-terpyridine; L = 1-methylimidazole-N3 (I), 1-methyl-1,2,4-triazole-N4 (II), 1-methyltetrazole-N3 (III), or 3-methylpyridine-N1 (IV)) and the respective geometry-optimized structures Io-IVo. Whereas this energy difference is larger than 70 kJ mol⁻¹ for compounds I, II, and IV, it amounts to only 0.8 kJ mol⁻¹ for the tetrazole-containing complex III, which is stabilized by two intramolecular C-H?N hydrogen bonds. Of all complexes under investigation, only the terpyridine-metal ion-tetrazole system with N3-coordinated tetrazole appears to be suited for an application in terms of a metal-mediated base pair in a metal-modified oligonucleotide.     

Stereosensitive formation and interconversion of sulfur-bridged cobalt(III)-mercury(II) polynuclear complexes with d- and/or l-penicillaminates

The reaction of trans(N)-[Co(d-pen)₂]⁻ (pen = penicillaminate) with HgCl₂ or HgBr₂ in the molar ratios of 1:1 gave the sulfur-bridged heterodinuclear complex, [HgX(OH₂){Co(d-pen)₂}] (X = Cl (1a) or Br (1b)). A similar reaction in the ratio of 2:1 produced the trinuclear complex, [Hg{Co(d-pen)₂}₂] (1c). The enantiomers of 1a and 1c, [HgCl(OH₂){Co(l-pen)₂}] (1a′) and [Hg{Co(l-pen)₂}₂] (1c′), were also obtained by using trans(N)-[Co(l-pen)₂]⁻ instead of trans(N)-[Co(d-pen)₂]⁻. Further, the reaction of cis · cis · cis-[Co(d-pen)(l-pen)]⁻ with HgCl₂ in the molar ratio of 1:1 resulted in the formation of [HgCl(OH₂){Co(d-pen)(l-pen)}] (2a). During the formations of the above six complexes, 1a, 1b, 1c, 1a′, 1c′, and 2a, the octahedral Co(III) units retain their configurations. On the other hand, the reaction of cis · cis · cis-[Co(d-pen)(l-pen)]⁻ with HgCl₂ in the molar ratio of 2:1 gave not [Hg{Co(d-pen)(l-pen}₂] but [Hg{Co(d-pen)₂}{Co(l-pen)₂}] (2c), accompanied by the ligand-exchange on the terminal Co(III) units. The X-ray crystal structural analyses show that the central Hg(II) atom in 1c takes a considerably distorted tetrahedral geometry, whereas that in 2c is of an ideal tetrahedron. The interconversion between the complexes is also examined. The electronic absorption, CD, and NMR spectral behavior of the complexes is discussed in relation to the crystal structures of 1c and 2c.     

New insight in coordination of vic-dioximes: Bis- and tris(E,E-dioximato)Ni(II) complexes

N,N′-Bis[allylamino]glyoxime, N,N′-bis[anilino]glyoxime, and N,N′-bis[1,2,3,4-tetrahydro-5-naphthalenamino]glyoxime have been prepared from corresponding amines and (E,E)-dichloroglyoxime. These ligands gave orange-red compound with NiCl₂ in less acidic medium (pH ∼ 5) that are bis(E,E-dioximato)nickel(II) complexes {[(E,E)-Ni(HL)₂]} (1a-3a) and green compounds in acidic medium (pH ∼ 2) that are tris(E,E-dioximato)nickel(II) dichloride complexes {[(E,E)-Ni(LH₂)₃]Cl₂} (1b-3b). The crystal structures of all complexes have been determined by X-ray diffraction on a single crystal. The study of absorption spectra of these two types of complexes shows that they may be converted to each other by addition of acids (1a-3a) or bases (1b-3b) and there is no way for the amphi form.     

Synthesis, spectroscopic properties and structural characterisation of Pd(II) and Pt(II) complexes with 1,3,5-pyrazole derived ligands. Rotation around the metal-N bond

Reactions of ligands 1-ethyl-5-methyl-3-phenyl-1H-pyrazole (L¹) and 5-methyl-1-octyl-3-phenyl-1H-pyrazole (L²) with [PdCl₂(CH₃CN)₂ and K₂PtCl₄ gave complexes trans-[MCl₂(L)₂] (L = L¹, L²). The new complexes were characterised by elemental analyses, conductivity measurements, infrared, ¹H and ¹³C{¹H} NMR spectroscopies and X-ray diffraction. The NMR study of the complex [PdCl₂(L¹)₂], in CDCl₃ solution, is consistent with a very slow rotation of ligands around the Pd-N bond, so that two conformational isomers can be observed in solution (syn and anti). Different behaviour is observed for complexes [PdCl₂(L²)₂] and [PtCl₂(L)₂] (L = L¹, L²), which present an isomer in solution at room temperature (anti). The crystal structure of [PdCl₂(L¹)₂] complex is described, where the Pd(II) presents a square planar geometry with the ligands coordinated in a trans disposition.     

Complexes of N-thiophosphorylthioureas RNHC(S)NHP(S)(OiPr)2 (HL) (R = pyridin-2-yl, pyridin-3-yl, 6-amino-pyridin-2-yl) with copper(I): Crystal structures of Cu(PPh3)nL (n = 1, 2)

Reaction of the potassium salts of N-thiophosphorylated thioureas of common formula RNHC(S)NHP(S)(OiPr)₂ [R = pyridin-2-yl (HL^a), pyridin-3-yl (HL^b), 6-amino-pyridin-2-yl (HL^c)] with Cu(PPh₃)₃I in aqueous EtOH/CH₂Cl₂ leads to mononuclear [Cu(PPh₃)₂L^a,b-S,S′] (1, 2) and [Cu(PPh₃)L^c-S,S′] (3) complexes. Using copper(I) iodide instead of Cu(PPh₃)₃I, polynuclear complexes [Cu_n(L-S,S′)_n] (4-6) were obtained. The structures of these compounds were investigated by IR, ¹H, ³¹P{¹H} NMR spectroscopy, ES-MS and elemental analyses. The crystal structures of Cu(PPh₃)₂L^b (2) and Cu(PPh₃)L^c (3) were determined by single-crystal X-ray diffraction.     

Synthesis and transition metal complexes of 3,3-bis(1-vinylimidazol-2-yl)propionic acid, a new N,N,O ligand suitable for copolymerisation

The new N,N,O heteroscorpionate ligand 3,3-bis(1-vinylimidazol-2-yl)propionic acid (Hbvip) (5) was synthesised in five steps starting from 1-vinylimidazole. This ligand is closely related to 3,3-bis(1-methylimidazol-2-yl)propionic acid (Hbmip), but contains two vinyl linker groups which can be used for radical-induced polymerisation reactions. The κ³-N,N,O coordination behaviour of 5 was proven by the synthesis of the tricarbonyl complexes [Re(bvip)(CO)₃] (6), [Mn(bvip)(CO)₃] (7) and [Cu(bvip)₂] (8). To obtain good yields of 6, it was synthesised in water instead of THF. The ligand as well as all three complexes were characterised by X-ray crystallography. Copolymerisation of 5 with pure methyl methacrylate (MMA) or a combination of MMA and ethylene glycol dimethacrylate (EGDMA) led to the solid phases P1 and P2. Polymer-bound rhenium and manganese tricarbonyl complexes could be obtained by the reaction of deprotonated P1 with [MBr(CO)₅] (M = Re, Mn) and also by copolymerisation of 6 and 7 with MMA. In both cases, the facial tripodal binding behaviour was evidenced by IR spectra of the polymers. Furthermore, the content of metal incorporated in the polymers was determined by elemental analysis, AAS or ICP-OES measurements. Reaction of the deprotonated solid phase P1 with copper(II) chloride led to a blue solid-phase (P1-Cu). The UV-Vis absorption maximum of P1-Cu is found at 615 nm, which is almost identical to that found for 8. Thereby, it seems likely that P1 is flexible enough to form bisligand complexes with copper(II). This means that the copper centres act as a kind of crosslinking agents. In contrast, the heterogeneous reaction of P2 with copper(II) chloride yielded a lime green solid phase (P2-Cu). The bathochromic shift of the absorption maximum by 102 nm suggests one-sided bound copper centres.     

Structural comparison of (pentamethylcyclopentadienyl)iridium(III) azido complexes containing potentially N,S-bidentate N-heterocyclic thiolates: 2- or 8-quinolinethiolate and benzimidazole-2-thiolate

The crystal structures of mononuclear (azido)(pentamethylcyclopentadienyl)iridium(III) complexes bearing 2- or 8-quinolinethiolate (n-Sqn⁻), [Cp^∗Ir(N₃)(n-Sqn)] {n = 2 (1) or 8 (2); Cp^∗ = η⁵-C₅Me₅} have been determined by X-ray analysis. The 2-Sqn complex, 1, acquires severe steric strains in the four-membered κ²N,S chelate ring, while the 8-Sqn isomer, 2, forms a strain-free five-membered planar κ²N,S chelate ring. It has also been revealed that the corresponding benzimidazole-2-thiolate (Hbimt⁻) complex, which was obtained similarly to the above n-Sqn complexes from [Cp^∗Ir(N₃)₂]₂ and Na(Hbimt), takes an unsymmetrical dinuclear structure bridged by two Hbimt⁻ ligands with different bonding modes, [Cp^∗Ir(N₃){μ(S:N¹)-Hbimt}{μ(S:S)-Hbimt}Ir(N₃)Cp^∗] · MeOH (3).     

Synthesis, crystal structures and density functional theory study of dimeric copper(II) complexes of a tridentate Schiff-base ligand

Oxalate- or 4,4′-bipyridine-bridged dimeric copper(II) complexes, [Cu₂L₂(μ-ox)] (1) and [Cu₂L₂(μ-bipy)](BF₄)₂ (2) [where ox = oxalate, bipy = 4,4′-bipyridine, HL = N-(1H-pyrrol-2-ylmethylene)-2-pyridineethanamine, L⁻ = HL−H⁺], have been synthesised and characterised by elemental analysis, IR, UV-Vis and single crystal X-ray diffraction. Crystal structure determinations carried out on 1 and 2 reveal that 1 is an oxalate-bridged centrosymmetrical square pyramidal dimeric copper(II) complex while 2 is a 4,4′-bipyridine-bridged non-centrosymmetric square planar dinuclear copper(II) complex. Comparison of the optimised geometries with the corresponding crystal structures suggests that the B3LYP/LANL2DZ level can reproduce the structures of 1 and 2 on the whole. The electronic spectra of 1 and 2 predicted by B3LYP/LANL2DZ method show some blue shifts compared with their experimental data. Thermal analysis carried out on 1 shows that there is only one exothermal peak at about 260 °C and the residue is presumably Cu₂O₄N₆.     

Synthesis, characterization and magnetic properties of new homotrinuclear copper(II) complexes

Two new mononuclear bis(oxamato) complexes with the formula [nBu₄N]₂[M(nabo)] M = Ni (4), Cu (5), with nabo = 2,3-naphthalene-bis(oxamato) have been synthesized as precursors for trinuclear oxamato-bridged transition metal complexes. Starting from 5 the homo-trinuclear complex [Cu₃(nabo)(pmdta)₂(BF₄)](BF₄) · MeCN · Et₂O (7), with pmdta = N,N,N′,N″,N″-pentamethyldiethylenetriamine, has been prepared. The central N,N′-2,3-naphthalene bridge of 7 is so far the most extended π-conjugated bridge of trinuclear bis(oxamato) type transition metal complexes. The goal of this work was to verify the N,N′-2,3-naphthalene bridge of 7 on its magnetic properties in comparison to the N,N′-o-phenylene bridge of the related homo-trinuclear complex [Cu₃(opba)(pmdta)₂(NO₃)](NO₃) · 2MeCN (6) (opba = o-phenylene-bis(oxamato)). The crystal structures of 4-7 were solved. The magnetic properties of 6 and 7 were studied by susceptibility measurements versus temperature. For the intramolecular J parameter, values of −89 cm⁻¹ (6) and −113 cm⁻¹ (7) were obtained. The different J values are discussed based on the crystal structures of 6 and 7.