Regioselective C(sp2)-C(sp3) Coupling Mediated by Classical and Rollover Cyclometalation.

By taking advantage of a sequence of oxidative addition/reductive elimination reactions, Pt(II) cyclometalated derivatives are able to promote a rare C(sp2)-C(sp3) bond coupling, resulting in the production of novel methyl-substituted pyridines and bipyridines. Starting from 6-phenyl-2,2'-bipyridine, the step-by-step full sequence of reactions has been followed, leading to the unprecedented 3-methyl-6-phenyl-2,2'-bipyridine, which was isolated and fully characterized. The synthesis involves the following steps: (1) rollover cyclometalation to give the starting complex [Pt(N^C)(DMSO)Me]; (2) the synthesis of a more electron-rich complex [Pt(N^C)(PPh3)Me] by the substitution of DMSO with triphenylphosphine; (3) oxidative addition with methyl iodide to give the Pt(IV) complex [Pt(N^C)(PPh3)(Me)2(I)]; (4) iodide abstraction with silver tetrafluoborate to give an unstable pentacoordinate intermediate, which rapidly evolves through a carbon-carbon reductive coupling, forming a new C(sp3)-C(sp2) bond; (5) finally, the extrusion and characterization of the newly formed 3-methyl-6-phenyl-2,2'-bipyridine. The reaction has been therefore extended to a well-known classical cyclometalating ligand, 2-phenylpyridine, demonstrating that the method is not restricted to rollover derivatives. Following the same step-by-step procedure, 2-phenylpyridine was converted to 2-o-tolyl-pyridine, displaying the potential application of the method to the larger family of classical cyclometalated complexes. The application of this protocol may be useful to convert an array of heterocyclic compounds to their methyl- or alkyl-substituted analogs.

Classical vs. Non-Classical Cyclometalated Pt(II) Complexes.

Rollover cyclometalated complexes constitute a family of derivatives which differ from classical cyclometalated species in certain aspects. Various potential application fields have been developed for both classes of compounds, which have both similarities and differences. In order to uncover the relationships and distinctions between these two families of compounds, four Pt(II) cyclometalated complexes derived from 2-phenylpyridine (ppy) and 2,2'-bipyridine (bpy), assumed as prototypical ligands, were compared. For this study, an electron rich isostructural and isoelectronic pair of compounds, [Pt(N^C)Me(PPh3)], and an electron-poorer compound, [Pt(N^C)Cl(PPh3)] were chosen (N^C = ppy or bpy). DFT calculations, cyclic voltammetry, and UV-Vis spectra also helped to shed light into these species. Due to the presence of the more electronegative nitrogen in place of a C-H group, the rollover bpy-H ligand becomes a slightly weaker donor than the classical ppy-H ligand, and hence, generates (slightly) more stable cyclometalated complexes, lower energy frontier molecular orbitals, and electron-poorer platinum centers. On the whole, it was revealed that classical and rollover complexes have overall structural similarity, which contrasts to their somewhat different chemical behavior.

Differential pulse voltammetry and chronoamperometry as analytical tools for epinephrine detection using a tyrosinase-based electrochemical biosensor.

The main goal of the presented study was to design a biosensor-based system for epinephrine (EP) detection using a poly-thiophene derivative and tyrosinase as a biorecognition element. We compared two different electroanalytical techniques to select the most prominent technique for analyzing the neurotransmitter. The prepared biosensor system exhibited good parameters; the differential pulse (DPV) technique presented a wide linear range (1-20 µM and 30-200 µM), with a low detection limit (0.18 nM and 1.03 nM). In the case of chronoamperometry (CA), a high signal-to-noise ratio and lower reproducibility were observed, causing a less broad linear range (10-200 µM) and a higher detection limit (125 nM). Therefore, the DPV technique was used for the calculation of sensitivity (0.0011 µA mM-1 cm-2), stability (49 days), and total surface coverage (4.18 × 10-12 mol cm-2). The biosensor also showed very high selectivity in the presence of common interfering species (i.e. ascorbic acid, uric acid, norepinephrine, dopamine) and was successfully applied for EP determination in a pharmaceutical sample.

Synthesis and characterization of new Pd(ii) and Pt(ii) complexes with 3-substituted 1-(2-pyridyl)imidazo[1,5-a]pyridine ligands.

Several palladium(ii) and platinum(ii) complexes (1-20) of general formula [M(Ln)(X)(Y)] [M = Pd, X = Y = Cl (1-Cl-4-Cl), X = Y = OAc (1-OAc-4-OAc); M = Pt: X = Y = Cl (5-8); M = Pd, X = Cl, Y = CH3 (9-12); M = Pt, X = Cl, Y = CH3 (13-16) or X = Y = CH3 (17-20); n = 1-4] have been synthesized by reaction of different Pd(ii) and Pt(ii) derivatives with various 3-substituted 1-(2-pyridyl)-imidazo[1,5-a]pyridines; i.e.Ln = 1-(2-pyridyl)-3-arylimidazo[1,5-a]pyridine (aryl = Phenyl, L1; 2-o-Tolyl, L2; Mesityl, L3) and 1-(2-pyridyl)-3-benzylimidazo[1,5-a]pyridine (L4). Detailed spectroscopic investigation (including IR, mono- and bi-dimensional 1H NMR) and elemental analysis has been performed for all these species, allowing their complete characterization. Ln act as N,N-bidentate ligands and coordinate the metal centers in a chelate fashion through the pyridyl (Npy) and the pyridine-like nitrogen atom of the imidazo[1,5-a]pyridine group (Nim). The X-ray structural analysis performed on two of Pd(ii) and three Pt(ii) complexes, namely [Pd(L2)(CH3)Cl] (10), [Pd(L3)(CH3)Cl] (11) and [Pt(L1)Cl2] (5), [Pt(L4)Cl2] (8), [Pt(L2)(CH3)Cl] (14) confirmed the spectroscopic and analytical data. Finally DFT studies unveiled the structural reasons behind the inertia of the synthesised compounds toward metalation, identified as the higher angle steric strain in comparison with the analogous bipyridine complexes.

Rollover Cyclometalation as a Valuable Tool for Regioselective C-H Bond Activation and Functionalization.

Rollover cyclometalation constitutes a particular case of cyclometallation reaction. This reaction occurs when a chelated heterocyclic ligand loses its bidentate coordination mode and undergoes an internal rotation, after which a remote C-H bond is regioselectively activated, affording an uncommon cyclometalated complex, called "rollover cyclometalated complex". The key of the process is the internal rotation of the ligand, which occurs before the C-H bond activation and releases from coordination a donor atom. The new "rollover" ligand has peculiar properties, being a ligand with multiple personalities, no more a spectator in the reactivity of the complex. The main reason of this peculiarity is the presence of an uncoordinated donor atom (the one initially involved in the chelation), able to promote a series of reactions not available for classic cyclometalated complexes. The rollover reaction is highly regioselective, because the activated C-H bond is usually in a symmetric position with respect to the donor atom which detaches from the metal stating the rollover process. Due to this novel behavior, a series of potential applications have appeared in the literature, in fields such as catalysis, organic synthesis, and advanced materials.

Position Impact of Hydroxy Groups on Spectral, Acid-Base Profiles and DNA Interactions of Several Monohydroxy Flavanones.

Structure-related biological activities of flavanones are still considered largely unexplored. Since they exhibit various medicinal activities, it is intriguing to enter deeper into their chemical structures, electronic transitions or interactions with some biomolecules in order to find properties that allow us to better understand their effects. Little information is available on biological activity of flavanone and its monohydroxy derivatives in relation to their physicochemical properties as spectral profiles, existence of protonated/deprotonated species under pH changes or interaction with Calf Thymus DNA. We devoted this work to research demonstrating differences in the physicochemical properties of the four flavanones: flavanone, 2'-hydroxyflavanone, 6-hydroxyflavanone and 7-hydroxyflavanone and linking them to their biological activity. Potentiometric titration, UV-Vis spectroscopy were used to investigate influence of pH on acid-base and spectral profiles and to propose the mode of interaction with DNA. Cyclic voltammetry was applied to evaluate antioxidant potentiality and additionally, theoretical DFT(B3LYP) method to disclose electronic structure and properties of the compounds. Molecular geometries, proton affinities and pKa values have been determined. According to computational and cyclic voltammetry results we could predict higher antioxidant activity of 6-hydroxyflavanone with respect to other compounds. The values of Kb intrinsic binding constants of the flavanones indicated weak interactions with DNA. Structure-activity relationships observed for antioxidant activity and DNA interactions suggest that 6-hydroxyflavanone can protect DNA against oxidative damage most effectively than flavanone, 2'-hydroxyflavanone or 7-hydroxyflavanone.

New Variations on the Theme of Gold(III) C∧N∧N Cyclometalated Complexes as Anticancer Agents: Synthesis and Biological Characterization.

A series of novel (C∧N∧N) cyclometalated AuIII complexes of general formula [Au(bipydmb-H)X][PF6] (bipydmb-H = C∧N∧N cyclometalated 6-(1,1-dimethylbenzyl)-2,2'-bipyridine) were prepared with a range of anionic ligands X in the fourth coordination position, featuring C (alkynyl)-, N-, O-, or S-donor atoms. The X ligands are varied in nature and include three coumarins, 4-ethynylaniline, saccharine, and thio-ß-d-glucose tetraacetate, the tripeptide glutathione (GSH), and a coumarin-substituted amide derived from 4-ethynylaniline. The gold(I) complex [Au(C2ArNHCOQ)(PPh3)] (HC2ArNHCOQ = N-(4-ethynylphenyl)-2-oxo-2 H-chromene-3-carboxamide) was also prepared for comparison. The new compounds were fully characterized by means of analytical techniques, including NMR, absorption, and emission spectroscopy. The crystal structures of three cyclometalated AuIII complexes and of the AuI derivative were solved by single-crystal X-ray diffraction. The antiproliferative activity of the new AuIII cyclometalated derivatives was evaluated against cancer cells in vitro. According to the obtained results, only complexes 3-PF6 and 5-PF6, featuring coumarins as ancillary ligands and endowed with high redox stability in solution, display antiproliferative effects, with 5-PF6 being the most potent, while all of the others are scarcely active to nonactive in the selected cell lines. In order to study the reactivity of the compounds with biomolecules, the interaction of complexes 3-PF6 and 5-PF6 with the protein cytochrome c and the amino acids cysteine and histidine was analyzed by electrospray ionization mass spectrometry (ESI MS), showing adduct formation only with Cys after at least 1 h incubation. Furthermore, the parent hydroxo complex [Au(bipydmb-H)(OH)][PF6] (1OH-PF6) was investigated in a competitive assay to determine the protein vs oligonucleotide binding preferences by capillary zone electrophoresis (CZE) coupled to ESI-MS. Of note, the compound was found to selectively form adducts with the oligonucleotide over the protein upon ligand exchange with the hydroxido ligand. Adduct formation occurred within the first 10 min of incubation, demonstrating the preference of 1OH-PF6 for nucleotides in this setup. Overall, the obtained results point toward the possibility to selectively target DNA with gold(III) organometallics.

Physicochemical, antioxidant, DNA cleaving properties and antimicrobial activity of fisetin-copper chelates.

Fisetin (3,3',4',7-tetrahydroxyflavone) metal chelates are of interest as this plant polyphenol has revealed broad prospects for its use as natural medicine in the treatment of various diseases. Metal interactions may change or enhance fisetin biological properties so understanding fisetin metal chelation is important for its application not only in medicine but also as a food additive in nutritional supplements. This work was aimed to determine and characterize copper complexes formed in different pH range at applying various metal/ligand ratios. Fisetin and Cu(II)-fisetin complexes were characterized by potentiometric titrations, UV-Vis (Ultraviolet-visible spectroscopy), EPR, ESI-MS, FTIR and cyclic voltammetry. Their effects on DNA were investigated by using circular dichroism, spectrofluorimetry and gel electrophoresis methods. The copper complex with the ratio of Cu(II)/fisetin 1/2 exhibited significant DNA cleavage activity, followed by complete degradation of DNA. The influence of copper(II) ions on antioxidant activity of fisetin in vitro has been studied using DPPH, ABTS and mitochondrial assays. The results have pointed out that fisetin or copper complexes can behave both as antioxidants or pro-oxidants. Antimicrobial activity of the compounds has been investigated towards several bacteria and fungi. The copper complex of Cu(II)/fisetin 1/2 ratio showed higher antagonistic activity against bacteria comparing to the ligand and it revealed a promising antifungal activity.

[Au(pyb-H)(mnt)]: A novel gold(III) 1,2-dithiolene cyclometalated complex with antimicrobial activity (pyb-H=C-deprotonated 2-benzylpyridine; mnt=1,2-dicyanoethene-1,2-dithiolate).

The novel heteroleptic cyclometalated complex [AuIII(pyb-H)(mnt)] (1; pyb-H=C-deprotonated 2-benzylpyridine; mnt =1,2-dicyanoethene-1,2-dithiolate) was tested against a panel of ten Gram positive (belonging to the Staphylococcus, Streptococcus spp. and Bacillus clausii), Gram negative (E. coli, K. pneumoniae, P. aeruginosa) bacteria and three yeasts belonging to the Candida spp. Complex 1 showed a remarkable bacteriostatic antimicrobial activity against staphylococci, with Minimum Inhibitory Concentration (MIC) values of 1.56 and 3.13µg/mL for S. haemoliticus and S. aureus, respectively. Spectroscopic and electrochemical measurements, supported by Density Functional Theory (DFT) calculations, were exploited to fully investigate the electronic structure of complex 1 and its relationship with the antimicrobial activity.

Cytotoxic properties of a new organometallic platinum(II) complex and its gold(I) heterobimetallic derivatives.

A novel platinum(ii) organometallic complex, [Pt(pbi)(Me)(DMSO)], bearing the 2-(2'-pyridyl)-benzimidazole (pbiH) ligand, was synthesized and fully characterized. Interestingly, the reaction of this organometallic platinum(ii) complex with two distinct gold(i) phosphane compounds afforded the corresponding heterobimetallic derivatives with the pbi ligand bridging the two metal centers. The antiproliferative properties in vitro of [Pt(pbi)(Me)(DMSO)] and its gold(i) derivatives as well as those of the known coordination platinum(ii) and palladium(ii) complexes with the same ligand, of the general formula [MCl2(pbiH)], were comparatively evaluated against A2780 cancer cells, either sensitive or resistant to cisplatin. A superior biological activity of the organometallic compound clearly emerged compared to the corresponding platinum(ii) complex; the antiproliferative effects are further enhanced upon attaching the gold(i) triphenylphosphine moiety to the organometallic Pt compound. Remarkably, these novel metal species are able to overcome nearly complete resistance to cisplatin. Significant mechanistic insight into the study compounds was gained after investigating their reactions with a few representative biomolecules by electrospray mass spectrometry and X-ray crystallography. The obtained results are comprehensively discussed.

Chiral cyclometalation of 6-(1-phenylbenzyl)-2,2'-bipyridine.

A new bipyridine ligand, 6-(1-phenylbenzyl)-2,2'-bipyridine, has been prepared by a multistep synthesis starting from the corresponding substituted pyridine. The coordinating properties of the new ligand have been tested with two d(8) metal ions, Pt(ii) and Pd(ii), to give the cyclometalated complexes [Pt(N,N,C)Cl] and [Pd(N,N,C)Cl], where N,N,C is a terdentate deprotonated bipyridine containing a new stereogenic carbon atom directly generated by C-H bond activation. The single-crystal of the platinum complex has been solved by X-ray diffraction. DFT calculations confirm the presence of a PtH interaction that stabilizes one of the two possible conformers by 14.7 kJ mol(-1) for Pt and 12.9 kJ mol(-1) for Pd. The energy barrier to pass from one conformer to the other is 25.4 and 23.8 kJ mol(-1) respectively. Under different reaction conditions, regioselective activation of a pyridine C-H bond gave the less common cyclometalated rollover complex [Pt(L-H)Me(DMSO)], which was isolated and characterised.

Assembly of symmetrical and unsymmetrical platinum(II) rollover complexes with bidentate phosphine ligands.

The reaction of the cyclometalated rollover complex [Pt(bpy-H)(Me)(DMSO)] (bpy-H = cyclometalated 2,2'-bipyridine) with two diphosphines, dppm (1,1-bis(diphenylphosphino)methane) and dppe (1,2-bis(diphenylphosphino)ethane), was investigated. According to the reaction conditions, dppm behaves as a monodentate, bridging or chelated ligand, whereas dppe gave only chelated species. Some aspects of the reactivity of the isolated species were studied, including protonation with [H3O·18-crown-6][BF4] and coordination reactions of mononuclear complexes, obtaining, inter alia, rare examples of unsymmetrical organometallic species with bridging dppm.

Rollover-assisted C(sp2)-C(sp3) bond formation.

Rollover cyclometalation involves bidentate heterocyclic donors, unusually acting as cyclometalated ligands. The resulting products, possessing a free donor atom, react differently from the classical cyclometalated complexes. Taking advantage of a "rollover"/"retro-rollover" reaction sequence, a succession of oxidative addition and reductive elimination in a series of platinum(II) complexes [Pt(N,C)(Me)(PR3)] resulted in a rare C(sp(2))-C(sp(3)) bond formation to give the bidentate nitrogen ligands 3-methyl-2,2'-bipyridine, 3,6-dimethyl-2,2'-bipyridine, and 3-methyl-2-(2'-pyridyl)-quinoline, which were isolated and characterized. The nature of the phosphane PR3 is essential to the outcome of the reaction. This route constitutes a new method for the activation and functionalization of C-H bond in the C(3) position of bidentate heterocyclic compounds, a position usually difficult to functionalize.

Rollover cyclometalation with 2-(2'-pyridyl)quinoline.

Rollover cyclometalation of 2-(2'-pyridyl)quinoline, L, allowed the synthesis of the family of complexes [Pt(L-H)(X)(L')] and [Pt(L*)(X)(L')][BF4] (X = Me, Cl; L' = neutral ligand), the former being the first examples of Pt(II) rollover complexes derived from the ligand L. The ligand L* is a C,N cyclometalated, N-protonated isomer of L, and can also be described as an abnormal-remote pyridylene. The corresponding [Pt(L-H)(Me)(L')]/[Pt(L*)(Me)(L')](+) complexes constitute an uncommon Brønsted-Lowry acid-base conjugated couple. The species obtained were investigated in depth through NMR and UV-vis spectroscopy, cyclic voltammetry, and density functional theory (DFT) methods to correlate different chemico-physical properties with the nature of the cyclometalated ligand (e.g., L vs bipy or L* vs L) and of the neutral ligand (DMSO, CO, PPh3). The crystal structures of [Pt(L-H)(Me)(PPh3)], [Pt(L-H)(Me)(CO)] and [Pt(L*)(Me)(CO)][BF4] were determined by X-ray powder diffraction methods, the latter being the first structure of a Pt(II)-based, protonated, rollover complex to be unraveled. The isomerization of [Pt(L*)(Me)(PPh3)](+) in solution proceeds through a retro-rollover process to give the corresponding adduct [Pt(L)(Me)(PPh3)](+), where L acts as a classical N,N chelating ligand. Notably, the retro-rollover reaction is the first process, among the plethora of Pt-C bond protonolysis reactions reported in the literature, where a Pt-C(heteroaryl) bond is cleaved rather than a Pt-C(alkyl) one.

Synthesis, structural characterization, solution behavior, and in vitro antiproliferative properties of a series of gold complexes with 2-(2'-pyridyl)benzimidazole as ligand: comparisons of gold(III) versus gold(I) and mononuclear versus binuclear derivatives.

A variety of gold(III) and gold(I) derivatives of 2-(2'-pyridyl)benzimidazole (pbiH) were synthesized and fully characterized and their antiproliferative properties evaluated in a representative ovarian cancer cell line. The complexes include the mononuclear species [(pbi)AuX(2)] (X = Cl, 1; OAc, 2), [(pbiH)AuCl] (3), [(pbiH)Au(PPh(3))][PF(6)] (4-PF(6)), and [(pbi)Au(L)] (L = PPh(3), 5; TPA, 6), and the binuclear gold(I)/gold(I) and gold(I)/gold(III) derivatives [(PPh(3))(2)Au(2)(µ(2)-pbi)][PF(6)] (10-PF(6)), [ClAu(µ(3)-pbi)AuCl(2)] (7),and [(PPh(3))Au(µ(3)-pbi)AuX(2)][PF(6)] (X = Cl, 8-PF(6); OAc, 9-PF(6)). The molecular structures of 6, 7, and 10-PF(6) were determined by X-ray diffraction analysis. The chemical behavior of these compounds in solution was analyzed both by cyclic voltammetry in DMF and absorption UV-vis spectroscopy in an aqueous buffer. Overall, the stability of these gold compounds was found to be acceptable for the cellular studies. For all complexes, relevant antiproliferative activities in vitro were documented against A2780 human ovarian carcinoma cells, either resistant or sensitive to cisplatin, with IC(50) values falling in the low micromolar or even in the nanomolar range. The investigated gold compounds were found to overcome resistance to cisplatin to a large degree. Results are interpreted and discussed in the frame of current knowledge on cytotoxic and antitumor gold compounds.

Ru2+ complexes comprising terpyridine ligands appended with terthiophene chromophores: energy transfer and energy reservoir effect.

Two Ru(2+) complexes containing terpyridine ligands appended with terthiophene units connected by a methyleneoxy or an alkynyl bridge show very different luminescent behaviours: the former is non-luminescent at 298 K owing to a photoinduced energy transfer process to the terthiophene moiety, while the latter exhibits an extraordinary long excited state lifetime because of an energy reservoir effect.

Gold(III) six-membered N

The first six-membered gold(III) N^C^N pincer complex was obtained in good yield, under very mild conditions, by transmetalation of [Hg(κC-N^C^N)Cl] (N^CH^N = 1,3-bis(pyridin-2-ylmethyl)benzene, HL(1)) with Na[AuCl(4)]. The X-ray crystal structure of [Au(N^C^N)Cl][PF(6)] showed that the fused six-membered metallacycles each exist in a strongly puckered boat conformation. As shown by the (1)H NMR spectra in various solvents, the same structure is also retained in solution: no inversion of the six-membered metallacycles is observed in DMSO up to 95 °C. This correlates well with a reaction barrier of 17.5 kcal/mole, as determined by quantum chemical calculations. The reactivity of the present pincer complex is compared to that of the analogous 1,3-bis(2-pyridyl)benzene, HL(2), derivative, which has five-membered fused metallacycles. Sharp differences are found in the reactions with phosphines, such as PPh(3) and dppe (1,2-bis-diphenylphosphino-ethane), and with silver salts. Theoretical calculations were carried out on the two pincer complexes in order to try to understand these differences, and we found that the gold-chlorine bond is significantly stronger in the case of the complex containing five-membered metallacyclic rings.

Platinum(II) N-heterocyclic carbene complexes: coordination and cyclometallation.

Four different NHC ligands have been coordinated to Pt(II) centres; for the first time cyclometallation of the NHC ligand was observed, but only when the platinum centre had a DMSO and two methyl co-ligands. Cyclometallation resulted in the exclusive formation of five-membered rings, and the absence of any double cyclometallation reactions with appropriate ligands rules out the possibility of an oxidative addition type mechanism for the cyclometallation reaction.

Reactivity of 1,3-bis(2-pyridyl)benzene, N--CH--N, with gold(III) chlorides: salts, adducts and cyclometalated pincer derivatives. Crystal and molecular structures of [HN--CH--N][AuCl4], [Au(N--C--N)Cl][PF6] and [Au(N--C--N)Cl(PPh3)2][PF6].

The reaction of 1,3-bis(2-pyridyl)benzene, N--CH--N, with H[AuCl(4)] has been studied under different conditions. Mono- ([N--CH--NH][AuCl(4)]) and di-protonated salts ([HN--CH--NH][AuCl(4)](2)), as well as an adduct, [(N--CH--N)(AuCl(3))(2)], have been isolated. Very rare cyclometalated pincer derivatives, [Au(N--C--N)Cl](+) have been obtained as different salts, either by transmetallation from the corresponding mercury(ii) derivative, [Hg(N--C--N)Cl], or by direct C-H activation. The structures in the solid state of [N--CH--NH][AuCl(4)] and [Au(N--C--N)Cl][PF(6)] have been solved by X-ray diffraction. Reaction of the pincer derivatives with PPh(3), dppm (bis(diphenylphosphino)methane) and dppe (1,2-bis(diphenylphosphino)ethane) occurs with displacement of the coordinated nitrogen atoms to afford [Au(N--C--N)(Cl)(PPh(3))(2)](+), [Au(N--C--N)(Cl)(dppm)(2)](+) and [Au(N--C--N)(Cl)(dppe)](+), respectively. The X-ray structure of [Au(N--C--N)(Cl)(PPh(3))(2)][PF(6)] confirms that the ligand N--C--N is only sigma-carbon bonded and the PPh(3) molecules are in a trans-arrangement. The pattern of the (31)P{(1)H}NMR spectrum of [Au(N--C--N)(Cl)(dppm)(2)](+), a pair of "triplets", deserves comments: the spectrum is not of the A(2)X(2) type but a case of a deceptively simple AA'XX' spin system.

Synthesis and properties of gold alkene complexes. Crystal structure of [Au(bipy(oXyl))(eta(2)-CH(2)=CHPh)](PF(6)) and DFT calculations on the model cation [Au(bipy)(eta(2)-CH(2)=CH(2))](+).

Unprecedented 16-electron gold(i) olefin complexes of general formula [Au(bipy(R,R'))(eta(2)-olefin)](PF(6)) and [Au(2)(bipy(R,R'))(2)(mu-eta(2):eta(2)-diolefin)](PF(6))(2) (bipy(R,R') = 6-substituted-2,2'-bipyridine) have been prepared by reaction of dinuclear gold(III) oxo complexes [Au(2)(bipy(R,R'))(2)(mu-O)(2)](PF(6))(2) with the appropriate olefin. The X-ray crystal structures of two mononuclear complexes (olefin = styrene) show in-plane coordination of the olefin and a C[double bond, length as m-dash]C bond distance considerably lengthened with respect to the free olefin. The spectroscopic properties of the complexes are discussed and compared with those of analogous d(10) metal derivatives. Both structural and spectroscopic information indicate a substantial contribution of pi-back-donation to the Au-olefin bond in the three-coordinate species. Theoretical calculations carried out at the hybrid-DFT level on the model compound [Au(bipy)(eta(2)-CH(2)[double bond, length as m-dash]CH(2))](+) show excellent agreement with the experimental findings giving in addition an estimate of a pi-back-bonding contribution higher than that of the sigma-bonding.