Tunable Interaction Strength and Nature of the S···Br Halogen Bonds in [(Thione)Br2] Systems

The strength and nature of the S···Br and Br···Br interactions were systematically tuned by altering the electron donor properties of the thione group. Three new halogen-bonded compounds, [(N-methylbenzothiazole-2-thione)Br2]·0.5CH2Cl2 (1), [(2(3H)-benzothiazolethione)Br2] (2), and [(2-benzimidazolethione)Br]·[Br3] (3), were synthesized and studied structurally by using X-ray crystallography and computationally by using charge density analysis based on QTAIM calculations. Analysis of the interaction strength indicated a formation of surprisingly strong S···Br halogen bonds in 1 (−104 kJ mol–1, and RBrS = 0.64) and 2 (−116 kJ mol–1, and RBrS = 0.63) with a substantial covalent contribution. …

Acid-Promoted Rearrangement of the Metalated Thienyl Rings in Dirhodium(II) Complexes with Thienyl Phosphines as Ligands

Several mono- and bis-cyclometalated compounds have been prepared and characterized from the thermal reaction of dirhodium(II) tetraacetate and tris(2-thienyl)phosphine, P(2-C4H3S)3 (1), in toluene/acetic acid mixtures. In refluxing acetic acid, the mono-cyclometalated compound Rh2(O2CCH3)3[(2-C4H2S)P(2-C4H3S)2] (CH3CO2H)2 (2A) isomerizes to Rh2(O2CCH3)3[(3-C4H2S)P(2-C4H3S)2](CH3CO2H)2 (2B), which results from the selective rearrangement of the metalated ring from a 2-thienyl to a 3-thienyl structure. In the same conditions, the bis-cyclometalated compounds of formula Rh2(O2CCH3)2[(2-C4H2S)P(2-C4H3S)2]2(CH3CO2H)2 and with head-to-tail (3AA) or head-to-head (4AA) configuration of the phosphi…

Inter- and intramolecular non-covalent interactions in 1-methylimidazole-2-carbaldehyde complexes of copper, silver, and gold

Abstract Three new imidazole compounds, [CuBr2(mimc)2] (1), [Ag(mimc)2][CF3SO3] (2), and [AuCl3(mimc)] (3) (mimc = 1-methylimidazole-2-carbaldehyde), have been synthesized, structurally characterized, and further analyzed using the QTAIM analysis. The compounds exhibit self-assembled 3D networks arising from intermolecular non-covalent interactions such as metallophilic interactions, metal-π contacts, halogens–halogen interactions, and hydrogen bonds. These weak interactions have a strong impact on the coordination sphere of the metal atoms and on the packing of compounds 1, 2, and 3.

Controlling the crystal growth of potassium iodide with a 1,1'-bis(pyridin-4-ylmethyl)-2,2'-biimidazole ligand (L) – formation of a linear [K4I4L4]n polymer with cubic [K4I4] core units

The crystal growth of potassium iodide was controlled by using the neutral organic 1,1′-bis(pyridin-4-ylmethyl)-2,2′-biimidazole (L) ligand as a modifier. The selected modifier allows the preservation of original cubic [K4I4] units and their arrangement into a linear ligand-supported 1D chain. The supported [K4I4] cubes are only slightly distorted compared to the cubes found in pure KI salt. The N–K binding of the ligand to the KI salt, as well as weak I⋯H, N⋯H, and N⋯I interactions, stabilizes the structure to create a unique 1D polymer of neutral potassium iodide ionic salt inside the [K4I4L4]n complex.

Solvent directs the dimensionality of Cu-dicyanoimidazoles

In this paper, we report one-pot reactions of the same reactants 4,5-dicyanoimidazole and CuI in different solvents. In pure MeCN, the reaction resulted in previously reported MOF structure [Cu(4,5-dicyanoimidazole)]n.(MeCN)0.5n (1). On the other hand, when MeCN/MeOH solvent mixture was used, a new coordination polymer [Cu(4,5-dicyanoimidazole)(MeCN)(CuI)]n (2) was formed. The crystallization yielded very different structures as determined by X-ray crystallography. In 1, the solvent molecule acetonitrile occupies the MOF pores via weak interactions, but in 2 it is coordinated to the metal center. Computational DFT calculations and topological charge density analysis were utilized to explore…

Dirhodium(II) compounds with bridging thienylphosphines: studies on reversible P,C/P,S coordination.

Monocyclometalated compound [Rh(2){(C(8)H(4)S)P(C(8)H(5)S)(2)}(CH(3)CO(2)H)(2)(O(2)CCH(3))(3)] (1 a) and bis-cyclometalated compound [Rh(2){(C(8)H(4)S)P(C(8)H(5)S)(2)}(2)(CH(3)CO(2)H)(2)(O(2)CCH(3))(2)] (2 a) have been isolated from the reaction of dirhodium tetraacetate and tris(2-benzo[b]thienyl)phosphine (2 BTP) using low acidic solutions. By contrast, in pure acetic acid the reaction of Rh(2)(O(2)CCH(3))(4) with 2 BTP and tris(2-thienyl)phosphine (2 TP), followed by replacement of the axial acetate ligands by chlorides, led to [Rh(2){(2-C(8)H(5)S)P(2-C(8)H(5)S)(2)}(2)Cl(2)(O(2)CCH(3))(2)] (3 b) and [Rh(2){(2-C(4)H(3)S)P(C(4)H(3)S)(2)}(2)Cl(2)(O(2)CCH(3))(2)] (5 b), respectively. These n…

Role of C–H···Au and Aurophilic Supramolecular Interactions in Gold–Thione Complexes

The role of noncovalent gold–hydrogen and aurophilic interactions in the formation of extended molecular systems of gold complexes was studied. Three new gold compounds with a heterocyclic thione ligand N-methylbenzothiazole-2-thione (mbtt), namely, [AuCl(mbtt)] (1), [AuBr(mbtt)] (2), and [Au(mbtt)2][AuI2]1–n[I3]n (3), were synthesized and characterized. The halide ligand had a considerable effect on the complex structures and thus to noncovalent contacts. Intermolecular C–H···Au and aurophilic Au···Au contacts were the dominant noncovalent interactions in structures 1–3 determining the supramolecular arrays of the gold complexes. In 1 and 2, unusual intermolecular C–H···Au gold–hydrogen co…

Persistence of oxidation state III of gold in thione coordination

Ligands N,N'-tetramethylthiourea and 2-mercapto-1-methyl-imidazole form stable Au(III) complexes [AuCl3(N,N'-tetramethylthiourea)] (1) and [AuCl3(2-mercapto-1-methyl-imidazole)] (2) instead of reducing the Au(III) metal center into Au(I), which would be typical for the attachment of sulfur donors. Compounds 1 and 2 were characterized by spectroscopic methods and by X-ray crystallography. The spectroscopic details were explained by simulation of the UV-Vis spectra via the TD-DFT method. Additionally, computational DFT studies were performed in order to find the reason for the unusual oxidation state in the crystalline materials. The preference for Au(III) can be explained via various weak in…

Potential anticancer heterometallic Fe-Au and Fe-Pd agents: Initial mechanistic insights

A series of gold(III) and palladium(II) heterometallic complexes with new iminophosphorane ligands derived from ferrocenylphosphanes [{Cp-P(Ph2)═N-Ph}2Fe] (1), [{Cp-P(Ph2)═N-CH2-2-NC5H4}2Fe] (2), and [{Cp-P(Ph2)═N-CH2-2-NC5H4}Fe(Cp)] (3) have been synthesized and structurally characterized. Ligands 2 and 3 afford stable coordination complexes [AuCl2(3)]ClO4, [{AuCl2}2(2)](ClO4)2, [PdCl2(3)], and [{PdCl2}2(2)]. The complexes have been evaluated for their antiproliferative properties in human ovarian cancer cells sensitive and resistant to cisplatin (A2780S/R), in human breast cancer cells (MCF7) and in a nontumorigenic human embryonic kidney cell line (HEK-293T). The highly cytotoxic trimeta…

Activation of the Cyano Group at Imidazole via Copper Stimulated Alcoholysis

Reactions of 4,5-dicyano-1-methylimidazole with CuX2 (X = Cl, Br) in alcohol solvents (ethanol and methanol) resulted in the formation of Cu(II) carboximidate complexes [CuCl2(5- cyano-4-C(OEt)N-1-methylimidazole)(EtOH)] (1), [Cu2(&micro

Dinuclear Palladium(II) and -(III) Compounds with O,O-Chelating Ligands. Room-Temperature Direct 2-Phenylation of 1-Methylindole

New dinuclear palladium(III) compounds of general formula Pd2[(C6H4)PPh2]2[O–O]2Cl2, O–O being chelating phenolates C6H4OC(O)R (R = CH3, 3a; R = C2H5, 3b; R = OPh, 3c) or acetylacetonates RC(O)CHC(O)R (R = CH3, 4a; R = CF3, 4b; R = C(CH3)3, 4c), have been obtained by oxidation with PhICl2 of the corresponding palladium(II) compounds. The stability of the new compounds has been studied by 31P NMR spectroscopy from 200 to 298 K. DFT calculations of the stability of the complexes have also been performed. In agreement with these calculations, only compound Pd2[(C6H4)PPh2]2[(CF3C(O)CHC(O)CF3]2Cl2, 6b, showed the highest thermal stability. 6b was characterized by X-ray diffraction methods, prese…

Modification of the supramolecular structure of [(thione)IY] (Y = Cl, Br) systems by cooperation of strong halogen bonds and hydrogen bonds

Four interhalogen complexes of heterocyclic thione ligands N-methylbenzothiazole-2-thione (mbtt) and 2(3)H-benzothiazole-thione (btt) with strong and tunable S⋯I halogen bonds were synthesized and characterized by X-ray single crystal diffraction. The study of the strength and nature of the interactions was supported by computational analysis using the Quantum Theory of Atoms in Molecules (QTAIM). Halogen bond and hydrogen bond directed self-assemblies of thione compounds were efficiently modified by the changes in the halogen bond donor and acceptor structures. In structures [(mbtt)ICl] (1) and [(mbtt)IBr] (2) the interplay of halogen bonds and hydrogen bonds between the thione hydrogens a…

Triazenides as Suitable Ligands in the Synthesis of Palladium Compounds in Three Different Oxidation States: I, II, and III

New orthometalated dinuclear triazenide palladium(II) compounds of the general formula Pd2[(C6H4)PPh2]2[R–N–N–N–R]2 (R = C6H5, 3a; o-BrC6H4, o-3b; o-MeOC6H4, o-3c; o-MeC6H4, o-3d ; p-BrC6H4, p-3b; p-MeOC6H4, p-3c; p-MeC6H4, p-3d) have been synthesized and structurally characterized. The characteristics of these compounds were compared with the isoelectronic formamidinate derivatives. These triazenide compounds have been suitable starting products in the synthesis of new not so common dinuclear palladium(I) compounds and new unusual palladium(III) ones. In the presence of an excess of the triazenide ligand, compounds o-3b and o-3c underwent a reduction process giving dinuclear palladium(I) c…

Benzothiazolethione complexes of coinage metals: from mononuclear complexes to clusters and polymers

Abstract The reactions of 2(3H)-benzothiazolethione (Hbtt) with [AuCl(tetrahydrothiophene)] and CuBr2 were studied, and found to yield a tetranuclear cluster compound [Au(btt)]4 [1] and a polymeric structure [CuBr(btt-btt)]n.nTHF (2). Crystallographic and spectroscopic methods were used for the characterization. In 1, the monoanionic ligand acted as a bidentate bridging N,S-donor giving a molecular cluster structure of an asymmetric coordination isomer. In the formation of 2, the ligand was dimerized by forming a S–S bond after deprotonation, and coordination via nitrogen donors to metal atoms took place leading to a polymeric structure. To clarify the diversity of reactions of Hbtt with co…

Self-assembly of square planar rhodium carbonyl complexes with 4,4-disubstituted-2,2′-bipyridine ligands

The impact of non-covalent interactions and reaction conditions on formation and self-assembly of ionic pairs of Rh complexes with 4,4’-disubstituted bipyridine ligands ([Rh(L1)(CO)2][Rh(CO)2Cl2])n (1), [Rh(L1)2Cl2][Rh(CO)2Cl2] (2), ([Rh(L1)(CO)2][Rh(CO)2Cl2][Rh(L1)(CO)2]n([Rh(CO)2(Cl)2])n) (3), ([Rh(L2)CO2] [Rh(CO)2Cl2])n∙EtOH (4), ([Rh(L2)(CO)2])n ([Rh(CO)2Cl2])n (5) (L1 = 4,4’-dimethyl-2,2’-bipyridine, L2 = 4,4’-diamine-2,2’-bipyridine) have been studied. Packing of square planar Rh complexes favor formation of one-dimensional chains. In structure 1, the polymeric chain is formed by the alternating cationic [Rh(L1)(CO)2]+ and the anionic [Rh(CO)2Cl2]- units leading to a neutral pseudo li…

Further orthometalated dinuclear palladium(iii) compounds with bridging N,S-donor ligands

New dinuclear palladium(III) compounds of general formula Pd2[(C6H4)PPh2]2[N-S]2Cl2, N-S being 2-mercaptopyridinate, 3a; 2-mercapto-6-methylpyridinate, 3b; 2-quinolinethiolate, 3c; 2-mercaptopyrimidinate, 3d; 1-methyl-1H-imidazole-2-thiolate, 3e; 1-methyl-1H-benzimidazole-2-thiolate, 3f; 2-mercaptobenzothiazolate, 3g and 5-mercapto-1-methyltetrazolate, 3h have been obtained by oxidation with PhICl2 of the corresponding palladium(II) counterparts. The stability of the new compounds has been studied by (31)P NMR spectroscopy from 200 to 298 K. Compounds 3f-h were relatively stable until room temperature and they have been synthesized and characterized by (31)P, (1)H and (13)C NMR spectroscopy…

Synthesis of Dirhodium(II) Complexes with Several Cyclometalated Thienylphosphines

The thermal reaction of dirhodium tetraacetate with tris(3-thienyl)phosphine (3TP), diphenyl(3-thienyl)phosphine (3TPPh2), and diphenyl(2-thienyl)phosphine (2TPPh2) gives rise to mono-cyclometalated and bis-cyclometalated compounds; the latter can have a head-to-head (H−H) or head-to-tail (H−T) configuration. Bis-cyclometalated compounds with H−T configuration can be prepared in high yield under photochemical conditions or by combining irradiation with subsequent thermal treatment in acetic acid. The reactivity order of aromatic ring C−H activation is phenyl < 2-thienyl ≪ 3-thienyl, which leads to a selective activation of the thienyl ring. Thus, only one mono-cyclometalated compound is obt…

The geometry of the silver 1,1′-dibenzyl-2,2′-biimidazole complexes

Abstract The argentophilic interactions and interactions of weakly coordinated nitrate and water with silver metal were studied by investigating the reaction of 1,1′-dibenzyl-2,2′-biimidazole (Bn2bim) with silver nitrate. Three new silver complexes [Ag4(Bn2bim)4(NO3)2]·4(CH3CH2OH)·2(NO3)·0.5(H2O) (1), [Ag4(Bn2bim)4(H2O)4]·4(NO3) (2) and [Ag4(Bn2bim)4(NO3)4]·6(CH2Cl2)·2(H2O) (3) were synthesized and characterized. Complexes 1-3 have rare tetranuclear twisted closed cyclic structure with four bridging biimidazoles and variable nitrate/water ratio. The interactions between the nitrate ligand and Ag as well as water ligands and Ag are considered to be weak due to the ease of exchanging them. Th…

Halogen bonds with coordinative nature: halogen bonding in a S–I+–S iodonium complex†

A detailed study of unexpectedly strong iodonium–sulfur halogen bonds in [I(2-imidazolidinethione)2]+ is presented. The interactions are characterized by single-crystal X-ray diffraction, charge density analysis based on QTAIM calculations, mass spectrometry, and NMR spectroscopy. The results, small RIS = 0.7 and high interaction energy of −60 kJ mol−1, support a coordinative nature of the halogen bond between the iodonium ion and the sp2 hybridized sulfur atoms.

Halogen bond preferences of thiocyanate ligand coordinated to Ru(II) via sulphur atom

Halogen bonding between [Ru(bpy)(CO)2(S-SCN)2] (bpy = 2,2’-bipyridine), I2 was studied by co-crystallising the metal compound and diiodine from dichloromethane. The only observed crystalline product was found to be [Ru(bpy)(CO)2(S-SCN)2]⋅I2 with only one NCS⋅⋅⋅I2 halogen bond between I2 and the metal coordinated S atom of one of the thiocyanate ligand. The dangling nitrogen atoms were not involved in halogen bonding. However, computational analysis suggests that there are no major energetic differences between the NCS⋅⋅⋅I2 and SCN⋅⋅⋅I2 bonding modes. The reason for the observed NCS⋅⋅⋅I2 mode lies most probably in the more favourable packing effects rather than energetic preferences between …

Fine-tuning halogen bonding properties of diiodine through halogen–halogen charge transfer – extended [Ru(2,2′-bipyridine)(CO)2X2]·I2 systems (X = Cl, Br, I)

The current paper introduces the use of carbonyl containing ruthenium complexes, [Ru(bpy)(CO)2X2] (X = Cl, Br, I), as halogen bond acceptors for a I2 halogen bond donor. In all structures, the metal coordinated halogenido ligand acts as the actual halogen bond acceptor. Diiodine, I2, molecules are connected to the metal complexes through both ends of the molecule forming bridges between the complexes. Due to the charge transfer from Ru–X to I2, formation of the first Ru–X⋯I2 contact tends to generate a negative charge on I2 and redistribute the electron density anisotropically. If the initial Ru–X⋯IA–IB interaction causes a notable change in the electron density of I2, the increased negativ…

Metallophilic interactions in stacked dinuclear rhodium 2,2'-biimidazole carbonyl complexes

Non-covalent metallophilic interactions were studied by investigating the stacking of two neutral rhodium complexes [Rh2I(R2bim)Cl2(CO)4] (R = Et, ethyl or Pr, propyl) in the solid state. Both dinuclear complexes formed infinite arrays of square planar d8 rhodium centres with intramolecular Rh⋯Rh distances of 3.1781(5) A (R = Et) and 3.1469(3) A (R = Pr) and the intermolecular Rh⋯Rh distances of 3.4345(6) A (R = Et) and 3.4403(3) A (R = Pr) between the adjacent molecules. The crystalline solids were stable and did not contain any solvent of crystallization. The effect of the metallophilic interactions on the absorption properties were studied using TD-DFT methods. The computational results …

Stability of Dinuclear Phosphane Palladium(III) Complexes: A DFT Approach

Computational density functional theory studies have been carried out for the dinuclear ortho-metalated palladium(III) compounds [Pd2{μ-(C6H4)PPh2}2{μ-(X1-X2)}2Cl2]. These studies have shown that the electronic and steric properties of the auxiliary ligands (X1-X2 = bridging (carboxylato) or chelating (phenolato/acetylacetonato) O,O-donor ligands, bridging N,N-donor ligands (triazenido/formamidinato/pyrazolato), and bridging N,S-donor ligands) lead to systematic trends in their stability, highlighting that (a) the electronic nature of the donor atoms trans to the P has a clear trend, the replacement of hard donor atoms (O, N) by softer S donors generally reducing the stability of the compou…

Determination of equilibrium constants and computational interaction energies for adducts of [Rh2(RCO2)(4-n)(PC)n] (n = 0-2) with Lewis bases.

Properties of dirhodium catalysts with cyclometalated aryl phosphine ligands have been studied. We report here the study of the acid−base reaction of Rh2(RCO2)2(PC)2(H2O)2 catalysts (PC = cyclometalated aryl phosphine) with different Lewis bases. The determination of the equilibrium constants of these reactions can be used to study to which extent the properties of the axial coordination site of the catalyst, considered the active site, are affected by modification of the metalated phosphines, the carboxylate ligands, or the incoming axial ligand. The trends in the computational density functional theory interaction energies show good agreement with the major trends in the equilibrium const…

Benzoato and Thiobenzoato Ligands in the Synthesis of Dinuclear Palladium(III) and ‐(II) Compounds: Stability and Catalytic Applications

New palladium(III) compounds of formula Pd2[(C6H4)PPh2]2[OXC(C6H5)]2Cl2 [3a (X = O); 3b (X = S)] were obtained by the oxidation of the analogous palladium(II) ones with PhICl2 and were characterized by 31P, 1H, and 13C NMR spectroscopy at 223 K. Compound 3a was also structurally characterized by single-crystal X-ray diffraction methods, which revealed a Pd–Pd distance of 2.5212(10) A. DFT calculations were conducted to study the stability of all of these new palladium(III) and -(II) compounds with focus on the influence of the OS substitution of the donor atom in the ligand. The palladium(II) compounds Pd2[(C6H4)PPh2]2[OXC(C6H5)]2 [2a (X = O), 2b (X = S)] were also tested as precatalyst in …

Noncovalent axial I∙∙∙Pt∙∙∙I interactions in platinum(II) complexes strengthen in the excited state

Abstract Coordination compounds of platinum(II) participate in various noncovalent axial interactions involving metal center. Weakly bound axial ligands can be electrophilic or nucleophilic; however, interactions with nucleophiles are compromised by electron density clashing. Consequently, simultaneous axial interaction of platinum(II) with two nucleophilic ligands is almost unprecedented. Herein, we report structural and computational study of a platinum(II) complex possessing such intramolecular noncovalent I⋅⋅⋅Pt⋅⋅⋅I interactions. Structural analysis indicates that the two iodine atoms approach the platinum(II) center in a “side‐on” fashion and act as nucleophilic ligands. According to c…

Weak aurophilic interactions in a series of Au(III) double salts.

In this work, several new examples of rare AuIII⋯AuIII aurophilic contacts are reported. A series of gold(III) double salts and complexes, viz. [AuX2(L)][AuX4] (L = 2,2′-bipyridyl, X = Cl 1, Br 2; L = 2,2′-bipyrimidine, X = Cl 3, Br 4; L = 2,2′-dipyridylamine, X = Cl 5, Br 6), [AuX3(biq)] (biq = 2,2′-biquinoline, X = Cl 7, Br 8), [LH][AuX4] (L = 2,2′-bipyridyl, X = Cl 9; L = 2,2′-bipyrimidine, X = Cl 12; L = 2,2′-dipyridylamine, X = Cl 14, Br 15; L = 2,2′-biquinoline, X = Cl 17, Br 18), [AuBr2(bpy)]2[AuBr4][AuBr2] 10, [AuCl2(bpm)][AuCl2] 11, (bpmH)2[AuBr4][AuBr2] 13, and (dpaH)[AuBr2] 16 (1, 2, and 7 were reported earlier) was synthesized by coordination of a particular ligand to the AuIII …

Concerted halogen and hydrogen bonding in [RuI2(H2dcbpy)(CO)2]···I2···(CH3OH)···I2···[RuI2(H2dcbpy)(CO)2].

A new type of concerted halogen bond-hydrogen bond interaction was found in the solid state structure of [RuI(2)(H(2)dcbpy)(CO)(2)]···I(2)···(MeOH)···I(2)···[RuI(2)(H(2)dcbpy)(CO)(2)]. The iodine atoms of the two I(2) molecules interact simultaneously with each other and with the OH group of methanol of crystallization. The interaction was characterized by single crystal X-ray measurements and by computational charge density analysis based on DFT calculations.

Halogen bonding—a key step in charge recombination of the dye-sensitized solar cell

The halogen bonding between [Ru(dcbpy)(2)(SCN)(2)] dye and I(2) molecule has been studied. The ruthenium complex forms a stable [Ru(dcbpy)(2)(SCN)(2)]···I(2)·4(CH(3)OH) adduct via S···I interaction between the thiocyanate ligand and the I(2) molecule. The adduct can be seen as a model for one of the key intermediates in the regeneration cycle of the oxidized dye by the I(-)/I(3)(-) electrolyte in dye sensitized solar cells.

Neutral one-dimensional metal chains consisting of alternating anionic and cationic rhodium complexes.

The metallophilic interactions were investigated within chains of oppositely charged rhodium carbonyl complexes. The cationic [Rh(CO)(2)(L)](+) (L = 2,2'-bipyridine and 1,10-phenanthroline) and anionic [RhCl(2)(CO)(2)](-) units were self-assembled into one dimensional rhodium chains supported by electrostatic interactions. The array of Rh centers in {[Rh(CO)(2)(2,2'-bpy)][RhCl(2)(CO)(2)]}(n) was found to be nearly linear with a Rh···Rh···Rh angle of 170.927(11)° and Rh···Rh distances of 3.3174(5) Å and 3.4116(5) Å. The crystal structure of {[Rh(CO)(2)(1,10-phen)][RhCl(2)(CO)(2)]} consisted of two sets of crystallographically independent chains with slightly different Rh···Rh···Rh angles (17…

Pyrazole and Pyrazolate as Ligands in the Synthesis and Stabilization of New Palladium(II) and (III) Compounds.

The versatility of pyrazole/pyrazolate as ligands has allowed the synthesis and the structural characterization of four different types of new orthometalated palladium compounds, for which DFT calculations have been performed in order to investigate their relative stabilities. [Pd2{μ-(C6H4)PPh2}2{μ-(R,R'2pz)}2] (R = R' = H, 2a; R = Br, R' = H, 2b; R = CH3, R' = H, 2c; R = H, R' = CH3, 2d; R = Br, R' = CH3, 2e) compounds with exo-bidentate pyrazolatos are the first paddlewheel dinuclear palladium(II) compounds with pyrazolato bridging ligands described and characterized in the literature. In the process of the synthesis of 2a, a new tetranuclear intermediate compound, [Pd4{μ-(C6H4)PPh2}4(μ-p…

Dinuclear Ortho-Metalated Palladium(II) Compounds with N,N- and N,O-Donor Bridging Ligands. Synthesis of New Palladium(III) Complexes

New dinuclear ortho-metalated palladium(II) compounds with N,N′-diarylformamidinates, Pd2[(C6H4)PPh2]2[R′NC(H)NR′]2 (R′ = C6H5, 3a; R′ = p-CH3C6H4, 3b; R′ = p-CH3OC6H4, 3c) and N,O-donor ligands, Pd2[(C6H4)PPh2]2[N,O]2 (N,O = succinimidate (5), phtalimidate (6), 2-hydroxypyridinate (7), acetanilidate (8)) have been synthesized and characterized by NMR spectroscopy and X-ray diffraction methods. The oxidation with iodobenzene dichloride gave new and rare Pd26+ compounds, Pd2[(C6H4)PPh2]2[R′NC(H)NR′]2Cl2 (R′ = C6H5, 4a; R′ = p-CH3C6H4, 4b). DFT calculations on the Pd24+ → Pd26+ oxidation reaction show that the substituents on the amidinate N atoms have a greater effect on the reaction energy …

Dihalogens as Halogen Bond Donors

CCDC 1029115: Experimental Crystal Structure Determination

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CCDC 950098: Experimental Crystal Structure Determination

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CCDC 1029120: Experimental Crystal Structure Determination

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CCDC 1935019: Experimental Crystal Structure Determination

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CCDC 1501673: Experimental Crystal Structure Determination

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CCDC 1009210: Experimental Crystal Structure Determination

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CCDC 996516: Experimental Crystal Structure Determination

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CCDC 1029124: Experimental Crystal Structure Determination

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CCDC 1029116: Experimental Crystal Structure Determination

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CCDC 944605: Experimental Crystal Structure Determination

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CCDC 930540: Experimental Crystal Structure Determination

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CCDC 944602: Experimental Crystal Structure Determination

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CCDC 1921770: Experimental Crystal Structure Determination

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CCDC 1009213: Experimental Crystal Structure Determination

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CCDC 1009209: Experimental Crystal Structure Determination

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CCDC 1009215: Experimental Crystal Structure Determination

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CCDC 1052931: Experimental Crystal Structure Determination

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CCDC 1501676: Experimental Crystal Structure Determination

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CCDC 1029121: Experimental Crystal Structure Determination

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CCDC 996514: Experimental Crystal Structure Determination

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CCDC 930539: Experimental Crystal Structure Determination

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CCDC 1921768: Experimental Crystal Structure Determination

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CCDC 941941: Experimental Crystal Structure Determination

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CCDC 1921769: Experimental Crystal Structure Determination

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CCDC 1588805: Experimental Crystal Structure Determination

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CCDC 1029126: Experimental Crystal Structure Determination

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CCDC 950096: Experimental Crystal Structure Determination

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CCDC 941943: Experimental Crystal Structure Determination

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CCDC 1009214: Experimental Crystal Structure Determination

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CCDC 1029123: Experimental Crystal Structure Determination

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CCDC 1012801: Experimental Crystal Structure Determination

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CCDC 2115418: Experimental Crystal Structure Determination

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CCDC 996519: Experimental Crystal Structure Determination

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CCDC 1524888: Experimental Crystal Structure Determination

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CCDC 944603: Experimental Crystal Structure Determination

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CCDC 1900285: Experimental Crystal Structure Determination

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CCDC 1499191: Experimental Crystal Structure Determination

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CCDC 1501675: Experimental Crystal Structure Determination

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CCDC 941946: Experimental Crystal Structure Determination

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CCDC 1935022: Experimental Crystal Structure Determination

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CCDC 1029114: Experimental Crystal Structure Determination

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CCDC 1501674: Experimental Crystal Structure Determination

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CCDC 1823385: Experimental Crystal Structure Determination

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CCDC 950097: Experimental Crystal Structure Determination

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CCDC 1009208: Experimental Crystal Structure Determination

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CCDC 941945: Experimental Crystal Structure Determination

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CCDC 1009211: Experimental Crystal Structure Determination

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CCDC 944600: Experimental Crystal Structure Determination

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CCDC 941947: Experimental Crystal Structure Determination

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CCDC 1900284: Experimental Crystal Structure Determination

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CCDC 1823543: Experimental Crystal Structure Determination

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CCDC 1029122: Experimental Crystal Structure Determination

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CCDC 1052933: Experimental Crystal Structure Determination

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CCDC 1012800: Experimental Crystal Structure Determination

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CCDC 1012799: Experimental Crystal Structure Determination

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CCDC 941942: Experimental Crystal Structure Determination

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CCDC 1935020: Experimental Crystal Structure Determination

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CCDC 2115419: Experimental Crystal Structure Determination

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CCDC 941944: Experimental Crystal Structure Determination

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CCDC 1407541: Experimental Crystal Structure Determination

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CCDC 1029128: Experimental Crystal Structure Determination

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CCDC 996518: Experimental Crystal Structure Determination

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CCDC 796465: Experimental Crystal Structure Determination

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CCDC 1935018: Experimental Crystal Structure Determination

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CCDC 996517: Experimental Crystal Structure Determination

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CCDC 1935021: Experimental Crystal Structure Determination

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CCDC 1029117: Experimental Crystal Structure Determination

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CCDC 1921767: Experimental Crystal Structure Determination

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CCDC 944604: Experimental Crystal Structure Determination

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CCDC 1052932: Experimental Crystal Structure Determination

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CCDC 996515: Experimental Crystal Structure Determination

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CCDC 1029119: Experimental Crystal Structure Determination

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CCDC 996520: Experimental Crystal Structure Determination

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CCDC 944601: Experimental Crystal Structure Determination

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CCDC 1029113: Experimental Crystal Structure Determination

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CCDC 1029118: Experimental Crystal Structure Determination

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CCDC 1009212: Experimental Crystal Structure Determination

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CCDC 1029125: Experimental Crystal Structure Determination

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CCDC 941940: Experimental Crystal Structure Determination

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CCDC 1029127: Experimental Crystal Structure Determination

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