Ylidic Carbon Research Articles

Synthetic and theoretical study on novel N-ylidic complexes of mercury as new antibacterial agents

The novel structure of Hg(II) complexes including the pyridinium ylide C5H5NCHC(O)C6H4-m-Br (Y) were synthesized and reported in this study. In the first step, the pyridinium salt C5H5NCH2C(O)C6H4-m-Br (S) was produced by reacting 2,3′-dibromoactophenone and pyridine. then, treatment of S with K2CO3 gave the related pyridinium ylide Y. Finally, the reaction of Y with HgX2 and Hg(NO3)2·H2O leads to the formation of novel binuclear [HgY2][HgX4] (X=Cl (1); X=Br (2); X=I (3)) and polymeric [HgY(NO3)2]n (4) complexes. The structure of complex 2 was also determined by X-ray diffraction analysis. The obtained analyses proved the coordination through the ylidic carbon to metallic center. Additionally, Natural Bond Orbital (NBO), Energy Decomposition Analysis (EDA), and EDA-NOCV studies are also used to investigate the nature of metal–ligand bonding in the complexes. Finally, the antibacterial activity of 1–4 was also examined against Gram positive and negative represented significant levels of inhibitory potency respected to used standards.

Thermal Rearrangement of Thiocarbonyl-Stabilised Triphenylphosphonium Ylides Leading to (Z)-1-Diphenylphosphino-2-(phenylsulfenyl)alkenes and Their Coordination Chemistry.

While thiocarbonyl-stabilised phosphonium ylides generally react upon flash vacuum pyrolysis by the extrusion of Ph3PS to give alkynes in an analogous way to their carbonyl-stabilised analogues, two examples with a hydrogen atom on the ylidic carbon are found to undergo a quite different process. The net transfer of a phenyl group from P to S gives (Z)-configured 1-diphenylphosphino-2-(phenylsulfenyl)alkenes in a novel isomerisation process via intermediate λ5-1,2-thiaphosphetes. These prove to be versatile hemilabile ligands with a total of seven complexes prepared involving five different transition metals. Four of these are characterised by X-ray diffraction with two involving the bidentate ligand forming a five-membered ring metallacycle and two with the ligand coordinating to the metal only through phosphorus.

Selectivity Control of the Ligand Exchange at Carbon in α-Metallated Ylides as a Route to Ketenyl Anions.

α-Metallated ylides have recently been reported to undergo phosphine by CO exchange at the ylidic carbon atom to form isolable ketenyl anions. Systematic studies on the tosyl-substituted yldiides, R3 P=C(M)Ts (M=Li, Na, K), now reveal that carbonylation may lead to a competing metal salt (MTs) elimination. This side-reaction can be controlled by the choice of phosphine, metal cation, solvent and co-ligands, thus enabling the selective isolation of the ketenyl anion [Ts-CCO]M (2-M). Complexation of 2-Na by crown ether or cryptand allowed structure elucidation of the first free ketenyl anion [Ts-CCO]- , which showed an almost linear Ts-C-C linkage indicative for a pronounced ynolate character. However, DFT studies support a high charge at the ketenyl carbon atom, which is reflected in the selective carbon-centered reactivity. Overall, the present study provides important information on the selectivity control of ketenyl anion formation which will be crucial for future applications.

Selektivitätskontrolle des Ligandenaustauschs am Kohlenstoff in α‐metallierten Yliden als Zugang zu Ketenylanionen**

AbstractKürzlich berichteten wir, dass α‐metallierte Ylide einen Phosphan‐CO‐Ligandenaustausch eingehen und darüber Zugang zu isolierbaren Ketenylanion liefern. Systematische Studien an Tosyl‐substituierten Yldiiden der Form R3P=C(M)Ts (M=Li, Na, K) zeigen nun, dass die Carbonylierung auch zu einer konkurrierenden Metallsalzeliminierung (MTs) führen kann. Diese Nebenreaktion kann durch die Wahl des Phosphans, des Metallkations, des Lösungsmittels und der Zugabe geeigneter Coliganden kontrolliert werden, was die selektive Isolierung des Ketenylanions [Ts−CCO]M (2‐M) ermöglicht. Die Komplexierung von 2‐Na durch Kronenethern oder Kryptanden ermöglichte zudem die Strukturaufklärung des ersten freien Ketenylanions [Ts−CCO], welches eine annähernd lineare S−C−O‐Einheit aufweist, was auf einen höheren Anteil der Ynolat‐Grenzstruktur hindeutet. DFT‐Studien zeigen jedoch eine hohe negative Ladung am Ketenylkohlenstoff, was sich in der selektiven Reaktivität am C1‐Atom widerspiegelt. Die vorgestellten Ergebnisse liefern wichtige Informationen über die Selektivitätskontrolle der Carbonylierung von α‐metallierten Ylide, was für künftige Anwendungen unabdingbar ist.

Cyclic Sulfoxonium Ylides: Synthesis and Chemospecific Reactivity in the Catalytic Alkylation of Indoles

AbstractThe study of the reactivity of cyclic sulfoxonium ylides has been so far neglected, in particular for reactions that forms carbon‐carbon bond at the ylide carbon atom. Herein, we describe the synthesis of cyclic sulfoxonium ylides by palladium‐catalyzed intramolecular arylation and the reactivity of these ylides in the C3‐alkylation of indoles in the presence of either an acid catalyst or an iridium catalyst. This study revealed that acid catalysis is only efficient for cyclic sulfoxonium ylides in which the tether is a six‐membered lactone, whereas iridium catalysis was better suited to the reaction of cyclic sulfoxonium ylides in which the tether is a five‐membered ring ketone or lactone. The observed chemospecificity might be due to the relative basicity of the ylides under acid catalysis and to the steric hindrance around an iridium carbene intermediate when the reaction is conducted with the iridium catalyst.

Bending Enamine Patterns of Stabilized Pentalenes into “Polymethine Ylides”

We report the synthesis and structural study of 2-substituted 1,3-bis(dimethylamino)pentalenes. The two electrons donating substituents shift the formally anti-aromatic pattern toward more suitable polarized structures. A subtle steric trade-off can result either in planar cyclopentadienyl vinamidiniums or in distorted structures featuring a pyramidalized ylidic carbon adjacent to a stabilized π-conjugated iminium (polymethine). This latter pattern mimics a postulated activated distorted geometry for key Breslow intermediates in the active site of thiamine-dependent enzymes. It highlights how the energetic drive to avoid anti-aromaticity can be used to access models for unconventional distorted conformations of organic molecules.

Insights into the multifaceted applications of vinyl sulfoxonium ylides.

Sulfoxonium ylides are important synthetic precursors in various organic transformations. Their synthetic potential was well explored in the synthesis of various bioactive natural products and pharmaceuticals. Vinyl sulfoxonium ylide is a stabilized sulfoxonium ylide containing an electron-deficient alkene at the ylidic carbon. Similar to α-keto sulfoxonium ylides, these reagents can generate vinyl carbenes in the presence of metals under suitable conditions. These vinyl carbenes can be used for various organic transformations such as X-H (X = C, N, O, S) insertions, annulations, and rearrangement reactions. Due to the dipole structure of the vinyl sulfoxonium ylide, it can undergo electrophilic addition with electrophiles at the α-position. These reagents are used as synthons for various aromatic and heteroaromatic compound syntheses. Moreover, their stability and convenient handling make them potential replacements for thermally less stable vinyl diazo compounds. Herein, we provide an overview of early efforts in this area, with particular emphasis on our own recent development of vinyl sulfoxonium ylide-mediated transformations in the presence and absence of metal catalysis, and also give personal perspectives on the challenges and future scope for improving the application of vinyl sulfoxonium ylides.

Direct Observation of the Dynamics of Ylide Solvation by Hydrogen-bond Donors Using Time-Resolved Infrared Spectroscopy.

The photoexcitation of α-diazocarbonyl compounds produces singlet carbene intermediates that react with nucleophilic solvent molecules to form ylides. The zwitterionic nature of these newly formed ylides induces rapid changes in their interactions with the surrounding solvent. Here, ultrafast time-resolved infrared absorption spectroscopy is used to study the ylide-forming reactions of singlet carbene intermediates from the 270 nm photoexcitation of ethyl diazoacetate in various solvents and the changes in the subsequent ylide–solvent interactions. The results provide direct spectroscopic observation of the competition between ylide formation and C–H insertion in reactions of the singlet carbene with nucleophilic solvent molecules. We further report the specific solvation dynamics of the tetrahydrofuran (THF)-derived ylide (with a characteristic IR absorption band at 1636 cm–1) by various hydrogen-bond donors and the coordination by lithium cations. Hydrogen-bonded ylide bands shift to a lower wavenumber by −19 cm–1 for interactions with ethanol, −14 cm–1 for chloroform, −10 cm–1 for dichloromethane, −9 cm–1 for acetonitrile or cyclohexane, and −16 cm–1 for Li+ coordination, allowing the time evolution of the ylide–solvent interactions to be tracked. The hydrogen-bonded ylide bands grow with rate coefficients that are close to the diffusional limit. We further characterize the specific interactions of ethanol with the THF-derived ylide using quantum chemical (MP2) calculations and DFT-based atom-centered density matrix propagation trajectories, which show preferential coordination to the α-carbonyl group. This coordination alters the hybridization character of the ylidic carbon atom, with the greatest change toward sp2 character found for lithium-ion coordination.

Ylide-Substituted Phosphines: A Platform of Strong Donor Ligands for Gold Catalysis and Palladium-Catalyzed Coupling Reactions.

The development of homogeneous catalysts is strongly connected to the design of new, sophisticated ligands, which resolve limitations of a given reaction protocol by manipulating the electronic properties of the metal and its spatial environment. Phosphines are a privileged class of ligands that find applications in many catalytic transformations, ranging from hydrogenation reactions to hydroformylation and coupling chemistry. For many years, chemists have been trying to improve the efficiency, selectivity, and application of coupling reactions. The use of highly electron-rich and bulky phosphines was often associated with increased selectivity and efficiency and led to the development of a vast variety of electron-rich alkyl-substituted phosphines. However, this concept of increasing the ligand donor strength reaches its limits with the use of trialkyl-substituted phosphines with tri-tert-butylphosphine thus being one of the most active ligands for many years. In the course of our research efforts to use the special donor strength of ylides to stabilize electron-deficient, low-valent main group compounds, we realized that ylide-substituted phosphine (YPhos) ligands possess remarkably strong donor abilities. Moreover, the YPhos ligands are highly tunable by changing the nature of the groups on the phosphonium, phosphine, or central ylidic carbon atom. We thus obtained a ligand platform with donor capabilities ranging from PCy3 to even stronger donor abilities than N-heterocyclic carbenes, while being more sterically demanding than simple phosphines as well as many well-known biarylphosphine ligands.These properties led us to explore the applicability of the YPhos ligands in catalysis. In a series of recent reports, our group applied YPhos ligands in gold and palladium catalyzed reactions at catalytic loadings applicable for medium- to large-scale applications. The increased donor strength and unique architecture allowed for remarkable activities in a series of transformations at mild reactions conditions. For gold(I)-catalyzed reactions, we obtained turnover numbers (TONs) for the hydroamination of phenylacetylene with aniline of over 20 000. Also, more complex reactions were easily catalyzed with efficiencies greater than those of other known gold(I) catalysts. Similar efficacies were found in a series of palladium-catalyzed coupling reactions. In Buchwald-Hartwig aminations, unprecedented activities for the amination of aryl chlorides were reached at room temperature. The speed of formation of the catalytically active mono-YPhos palladium species allowed for some of the amination reactions to be completed in only a few minutes. Adjustment of the ligand design enabled the use of a large variety of different aryl and alkyl amines of different steric demands. Furthermore, the YPhos ligands in general showed high activities and selectivity in the coupling of a variety of carbon nucleophiles with aryl chlorides, bromides, and triflates. This enabled the development of efficient reaction protocols for the α-arylation of unhindered ketones and the coupling of Grignard and zinc reagents as well as the first efficient coupling of chloroarenes with alkyllithium compounds. This Account summarizes the recent development of YPhos ligands and their application in gold and palladium catalysis. We also hope to stimulate further use of this ligand platform in catalysis in the future.

Front Cover: Synthesis, Crystal and Electronic Structures of a Thiophosphinoyl‐ and Amino‐Substituted Metallated Ylide (ChemistryOpen 11/2021)

The Front Cover shows the structure of the newly reported, isolated metallated ylide. Due to the high negative charge at the ylidic carbon center this compound is „on fire“, but can be stabilized by smart molecular design. Structure analyses of the different alkali metal complexes combined with computational studies provide insights into the electronic structure of the compounds. More information can be found in the Communication by by Mike Jörges et al.

Synthesis, Crystal and Electronic Structures of a Thiophosphinoyl- and Amino-Substituted Metallated Ylide.

α‐Metallated ylides have revealed themselves to be versatile reagents for the introduction of ylide groups. Herein, we report the synthesis of the thiophosphinoyl and piperidyl (Pip) substituted α‐metallated ylide [Ph2(Pip)P=C−P(S)Ph2]M (M=Li, Na, K) through a four‐step synthetic procedure starting from diphenylmethylphosphine sulfide. Metallation of the ylide intermediate was successfully accomplished with different alkali metal bases delivering the lithium, sodium and potassium salts, the latter isolable in high yields. Structure analyses of the lithium and potassium compounds in the solid state with and without crown ether revealed different aggregates (monomer, dimer and hexamer) with the metals coordinated by the thiophosphoryl moiety and ylidic carbon atom. Although the piperidyl group does not coordinate to the metal, it significantly contributes to the stability of the yldiide by charge delocalization through negative hyperconjugation.

Ylide-Substituted Phosphines with a Cyclic Ylide-Backbone: Angle Dependence of the Donor Strength.

Ylide-substituted phosphines (YPhos) have been shown to be highly electron-rich and efficient ligands in a variety of palladium catalyzed transformations. Here, the synthesis and characterization of novel YPhos ligands containing a cyclic backbone architecture are reported. The ligands are easily synthesized from a cyclic phosphonium salt and the chlorophosphines Cy2PCl (L1) and Cy(FluMe)PCl (L2, with FluMe = 9-methylfluorenyl) and were characterized in both solution and solid states. The smaller PCy2-substituted ligand, L1, readily formed the biscoordinate L12Pd species when treated with Pd2(dba)3 and showed no activity in palladium-catalyzed amination reactions even when applied as defined palladium(II) η3-allyl, t-Bu-indenyl, or cinnamyl precursors. Bulkier fluorenyl-substituted ligand L2 similarly was inactive, despite its ability to form the stable monophosphine complex L2·Pd(dba). Assessment of the electronic properties by experimental and computational methods revealed that L1 and L2 are considerably less electron-rich than previously synthesized YPhos ligands. This was shown to be the result of the small P–C–S bond angle, which is sterically enforced due to the cyclic nature of the backbone. Density functional theory calculations revealed that the small angle results in an increased s-character of the lone pair at the ylidic carbon atom and leads to a polarization of the C–P bond toward the carbon atom, thus decreasing the electron density at the phosphorus atom. The results demonstrate the tunability of the donor strength of YPhos ligands by modification of the ligand backbone beyond simple changes of the substitution pattern and are thus important for future ligand design, with a careful balance of many factors to be considered to achieve catalytic activity.

New Pd‐phosphorus ylide complexes based on FC60 as heterogeneous nano‐catalyst for H/D exchange reaction

In this account, new Pd(0) complexes of phosphorus ylides based on fullerene C60 (FC60) were synthesized and utilized as the first fullerene‐based heterogeneous nano‐catalysts for H/D exchange reaction. Four new palladacyclopropa‐[60]fullerene complexes 1–4, [(η2‐C60)Pd(Y1–4)2] (Y1 = PPh3CHC(O)C6H4‐p‐NO2, Y2 = PPh3CHC(O)C6H4‐p‐CH3, Y3 = (p‐tolyl)3P‐CHC(O)C6H4‐p‐NO2, and Y4 = (p‐tolyl)3P‐CHC(O)C6H4‐p‐CH3), were prepared through dissolving the related α‐keto stabilized phosphorus ylide in toluene solution in the presence of FC60 and Pd (dba)2 (dba = dibenzylideneacetone). All of the complexes were characterized using Nuclear magnetic resonance (NMR) (1H, 13C, and 31P), Infrared spectroscopy (IR), Ultraviolet‐visible spectroscopy (UV‐visible), fluorescence, Electrospray Ionisation Mass Spectrometry (ESI‐MS), and Energy‐dispersive X‐ray spectroscopy (EDX) spectroscopies, and scanning electron microscopy (SEM) and TEM techniques. The data proved that FC60 and two ylides were coordinated to Pd(0) center through two hexagons and two ylidic carbon atoms, respectively. An evaluation was also performed to compare the catalytic activity of synthesized Pd complex 1 and a conventional heterogeneous catalyst, 10% Pd on carbon, in H/D exchange reaction. The results indicate that the process of H/D exchange reaction in aromatic rings of benzoic acid derivatives progressed more efficiently by Pd complex 1.

A novel structural type of conformationally fixed, mixed phosphonium-iodonium ylides based on phenoxaphosphinine

A synthetic approach to a novel type of phosphonium and mixed phosphonium-iodonium ylides containing a conformationally fixed phosphonium fragment is developed. New representatives of these families of chemical compounds based on cyclic phenoxaphosphinine were synthesized. One compound was structurally characterized by single-crystal X-ray diffraction. Based on the 1H NMR data, one can state that phosphonium ylide exists in solution in the form of two geometric isomers even at room temperature. This is indicative of pronounced double-bond character of the bond between the ylide carbon atom and the stabilizing carbomethoxy group.

Ruthenium(II)-Catalyzed Homocoupling of α-Carbonyl Sulfoxonium Ylides Under Mild Conditions: Methodology Development and Mechanistic DFT Study.

A mild ruthenium(II)-catalyzed homocoupling of α-carbonyl sulfoxonium ylides was developed and the detailed mechanism was understood based on DFT calculations in the current report. The catalytic system utilizes the α-carbonyl sulfoxonium ylide as both the directing group for ortho-sp2 C-H activation and the acylmethylating reagent for C-C coupling. Various substituents are compatible in the transformation and a variety of isocoumarin derivatives were synthesized at room temperature without any protection. The theoretical results disclosed that the full catalytic cycle contains eight elementary steps, and in all the cationic Ru(II) monomer is involved as the catalytic active species. The acid additive is responsible for protonation of the ylide carbon prior to the intramolecular nucleophilic addition and C-C bond cleavage. Interestingly, the intermediacy of free acylmethylation intermediate or its enol isomer is not necessary for the transformation.

Cu(I) Complexes of Multidentate N,C,N- and P,C,P-Carbodiphosphorane Ligands and Their Photoluminescence

A series of dinuclear copper(I) N,C,N- and P,C,P-carbodiphosphorane (CDP) complexes using multidentate ligands CDP(Py)2 (1) and (CDP(CH2PPh2)2 (13) have been isolated and characterized. Detailed structural information was gained by single-crystal XRD analyses of nine representative examples. The common structural motive is the central double ylidic carbon atom with its characteristic two lone pairs involved in the binding of two geminal L-Cu(I) fragments at Cu–Cu distances in the range 2.55–2.67 Å. In order to enhance conformational rigidity within the characteristic Cu–C–Cu triangle, two types of chelating side arms were symmetrically attached to each phosphorus atom: two 2-pyridyl functions in ligand CDP(Py)2 (1) and its dinuclear copper complexes 2–9 and 11, as well as two diphenylphosphinomethylene functions in ligand CDP(CH2PPh2)2 (13) and its di- and mononuclear complexes 14–18. Neutral complexes were typically obtained via the reaction of 1 with Cu(I) species CuCl, CuI, and CuSPh or via the salt elimination reaction of [(CuCl)2(CDP(Py)2] (2) with sodium carbazolate. Cationic Cu(I) complexes were prepared upon treating 1 with two equivalents of [Cu(NCMe)4]PF6, followed by the addition of either two equivalents of an aryl phosphine (PPh3, P(C6H4OMe)3) or one equivalent of bisphosphine ligands bis[(2-diphenylphosphino)phenyl] ether (DPEPhos), 4,5-bis(diphenylphosphino)-9,9-dimethylxanthene (XantPhos), or 1,1′-bis(diphenyl-phosphino) ferrocene (dppf). For the first time, carbodiphosphorane CDP(CH2PPh2)2 (13) could be isolated upon treating its precursor [CH(dppm)2]Cl (12) with NaNH2 in liquid NH3. A protonated and a deprotonated derivative of ligand 13 were prepared, and their coordination was compared to neutral CDP ligand 13. NMR analysis and DFT calculations reveal that the most stable tautomer of 13 does not show a CDP (or carbone) structure in its uncoordinated base form. For most of the prepared complexes, photoluminescence upon irradiation with UV light at room temperature was observed. Quantum yields (ΦPL) were determined to be 36% for dicationic [(CuPPh3)2(CDP(Py)2)](PF6)2 (4) and 60% for neutral [(CuSPh)2(CDP(CH2PPh2)2] (16).

Effective Control of the Electron‐donating Ability of Phosphines by using Phosphazenyl and Phosphoniumylidyl Substituents

Phosphoniumylidyl and phosphazenyl groups are effective substituents to increase the electron‐donating ability of tertiary phosphines. However, the influence of structural variations among those substituents on the electronic properties of the phosphines is little explored. Herein, we show that protonation of the ylidic carbon atom of phosphoniumylidyl phosphines increases the Tolman electronic parameter (TEP) by ΔTEP = 16.0–18.8 cm–1. Furthermore, phosphazenyl phosphines were synthesized with isopropyl groups (NP{iPr}3) and tetramethylguanidino groups (NP{tmg}3) at the phosphonium center. Determination of their TEP values reveals a remarkable low substituent parameter of χ = –18.5 cm–1 for the NP(tmg)3 group. In addition, we prepared the corresponding gold(I) complexes and determined their solid‐state structures using single‐crystal X‐ray diffraction studies to analyze the steric profile of the new phosphine ligands.

A Close Look to the Oxaphosphetane Formation along the Wittig Reaction: A [2+2] Cycloaddition?

The Wittig reaction between triphenylphosphine methylide and benzaldehyde has been studied both from conceptual and computational approaches. The supernucleophilic character of ylide accounts for the feasibility of the initial nucleophilic attack. The nature of bonding driving the formation of the first oxaphosphetane (OPA) intermediate in such a domino reaction is examined within a topological-based bonding evolution theory perspective. The sequence of the electronic flow associated to the changes in electron density supports a rationalization via two main electronic stages characterizing the single kinetic step: first, the C-C bond formation, which takes place via donation of electron density of the ylide carbon to the carbonyl carbon of benzaldehyde at a C-C distance of 2.02 Å, is formally associated to the transition state region; then, the P-O bond formation via the donation of electron density of the nonbonding region of the carbonyl oxygen to phosphorus at a P-O distance of 2.06 Å is located at the end of the reaction path. The detailed picture of bonding patterns suggests that the OPA formation in the Wittig mechanism can be better understood in terms of a two-stage one-step mechanism beyond molecular orbital considerations behind the traditionally accepted [2+2] cycloaddition proposal.

C, C coordination mode in comparison with C, P coordination mode in six and seven pallada- and platinacycle complexes of phosphorous ylide; synthesis, X-ray and theoretical studies

New symmetrical [p-CN-C6H4C(O)CH2PPh2(CH2)2PPh2CH2C(O)C6H4-p-CN]Br2(1) and unsymmetrical [PPh2(CH2)2PPh2CH2C(O)C6H4-p-CN]Br (2) phosphonium salts were prepared by reacting Bis(diphenylphosphino)ethane (dppe) with p-CN-C6H4C(O)CH2Br in acetone, in 1:2 and 1:1 ratios, respectively. Treatment of these salts with an appropriate alkali led to symmetrical p-CN-C6H4C(O)C(H)PPh2(CH2)2PPh2C(H)C(O)C6H4-p-CN (3) and unsymmetrical PPh2(CH2)2PPh2C(H)C(O)C6H4-p-CN (4) ylides.The reaction of 3 and 4 with [MCl2(cod)] (M = Pd or Pt; cod = 1,5-cyclooctadiene) in 1:1 ratio, using dichloromethane as a solvent, led to mononuclear seven membered metallocyclic ring complexes ([MCl2(p-CN-C6H4C(O)C(H)PPh2(CH2)2PPh2C(H)C(O)C6H4-p-CN)] (M = Pd (5) and Pt (6), having C,C coordination mode) and mononuclear six membered ring complexes [MCl2(PPh2(CH2)2PPh2C(H)C(O)C6H4-p-CN)] (M = Pd (7) and Pt (8), having P,C coordination mode), respectively. Characterization of the resulting compounds were performed by elemental analysis, IR, 1H,13C and 31P NMR spectroscopic methods. As well, the unequivocal structure of compound 5 (seven membered pallada-cycle complex) was characterized crystallographically. In the symmetrical complexes, with seven membered metallocyclic rings, the title ylide is coordinated to the metal through two ylidic carbon atoms. Using theoretical methods, Density-function theory (DFT) calculations at the BP86/def2-SVP level of theory, the structures of the unsymmetrical six membered pallada- and platinacyclic complexes were compared with the structures of the symmetrical seven membered pallada- and platinacyclic complexes. The strength and nature of donor−acceptor bonds between the phosphorus ylide (Y ligand) and MCl2 fragments in the [YMCl2] (M = Pd, Pt, Y = p-CN-C6H4C(O)C(H)PPh2(CH2)2PPh2C(H)C(O)C6H4-p-CN,PPh2(CH2)nPPh2C(H)C(O)C6H4-p-CN, n = 1–2, were carried out by Natural bond orbital analysis (NBO) and energy-decomposition analysis (EDA) as well as their natural orbitals for chemical valence (NOCV) variations.

Binuclear and polymeric Hg(II) complexes of an ambidentate phosphorus ylide: Synthesis, crystal structure, antibacterial activity, and theoretical studies

The new α‐keto‐stabilized phosphorus ylide Ph3PCHC(O)PhCN (Y) was synthesized by addition of triphenylphosphine to 2‐bromo‐4′‐cyanoacetophenone, followed by treatment with NaOH 10%. Reaction of ligand (Y) with methanolic solution of mercury(II) halides under mild conditions yielded the binuclear complexes [Y·HgX2]2 [X=Cl (1), Br (2), I (3)]. The new organic/inorganic composite polymer [Hg(NO3)2(Y)]n (4) was synthesized by the reaction of mercury(II) nitrate with the phosphorus ylide Y. Compounds synthesized were characterized by Fourier‐transform infrared, 1H, 31P, and 13C nuclear magnetic resonance spectroscopic methods, which confirmed the coordination of ylide to the metal center through the ylidic carbon atom. Single‐crystal X‐ray structures of phosphorus ylide Y and polymeric complex 4 were also determined and the crystallographic data of complex 4 showed that the title complex has an infinite one‐dimensional structure. Furthermore, the electronic and molecular structures of complexes 1–3 were investigated at the BP86/def2‐SVP level of theory, indicating an increasing trend for C→M bond lengths: Hg2I2 > Hg2Br2 > Hg2Cl2 in [Y→HgX2]2 (X = Cl, Br, I) complexes. In addition, the antibacterial activity of ligand Y and all complexes using the agar disc diffusion method was examined against both selected gram‐positive and gram‐negative bacteria. Results indicated that the ligand Y and complexes 1 and 4 show good antibacterial effect against gram‐positive bacteria tested; besides, the inhibition zones of complexes were significantly larger than those of chloramphenicol as standard.