Non-coordinating Research Articles

Coordination chemistry of a weakly coordinating carbanion

Carbanions are typically highly reactive species but can be efficiently stabilized to even function as stable weakly coordinating anions (WCA). We now report on the coordination chemistry of the recently introduced allyl anion 1, stabilized by ArF (ArF = 3,5-bis(trifluoromethyl)phenyl), triflyl substituents, with various s-block metals. A systematic crystallographic study on the s-block metal salts (Li-Cs, Ca) showed that the alkali metals have minimal impact on the anion, as indicated by the similar structural properties compared to the phosphonium salt of 1. In contrast, the calcium complex showed a slightly more pronounced distortion of the allyl symmetry due to stronger Ca–O interactions with the triflyl group. Additionally, the significance of the allyl moiety in stabilizing the carbanionic charge in 1 was demonstrated by comparing the structural parameters and charge distribution with those of an analogous C1-anion. Overall, these studies confirm the enhanced stability of 1 and its weak coordination tendency

Novel Silicate Platform as Weakly‐Coordinating Anions for Diverse Organometallic and Electrochemical Applications

Weakly‐coordinating anions (WCAs) are employed in a wide range of applications, but limitations remain, including high reactivity, limited redox window, complicated synthesis, high cost, low solublity, and low structural tunabililty. Herein, we report a new class of WCA based on alkyl or aryl (R) substituted silicates bearing fluorinated pinacolate ligands, "[RSiF24]‐". Anions bearing a variety of R groups were prepared, enabling facile tuning of sterics and solubility. A range of cations employed in chemical reactivity has been supported by these anions, including ether‐free alkali cations, Ag+, Ph3C+, Fc+, [NiI(COD)2]+. [Pd(dppe)(NCMe)Me]+ has been generated by salt metathesis or protonation of a metal‐alkyl bond, showcasing the ability of the RSiF24‐ anions to support applications in coordination chemistry and catalysis. Electrochemical studies on the [Bu4N]+ variant show an exceptionally wide stability window for the MeSiF24‐ anion of 7.5 V in MeCN. CV experiments demonstrate reversible Mg deposition and stripping.

Novel Silicate Platform as Weakly-Coordinating Anions for Diverse Organometallic and Electrochemical Applications.

Weakly-coordinating anions (WCAs) are employed in a wide range of applications, but limitations remain, including high reactivity, limited redox window, complicated synthesis, high cost, low solublity, and low structural tunabililty. Herein, we report a new class of WCA based onalkyl or aryl (R)substitutedsilicates bearingfluorinated pinacolate ligands,"[RSiF24]-".Anions bearing a variety of R groups were prepared, enabling facile tuning of sterics and solubility. A range of cations employed in chemical reactivity has been supported by these anions, including ether-free alkali cations, Ag+, Ph3C+, Fc+, [NiI(COD)2]+. [Pd(dppe)(NCMe)Me]+has been generated by salt metathesis or protonation of a metal-alkyl bond, showcasing the ability of theRSiF24-anions to support applications in coordination chemistry and catalysis. Electrochemical studies on the [Bu4N]+variant show an exceptionally wide stability window for theMeSiF24-anion of 7.5 V in MeCN. CV experiments demonstrate reversible Mg deposition and stripping.

Pushing redox potentials to highly positive values using inert fluorobenzenes and weakly coordinating anions

While the development of weakly coordinating anions (WCAs) received much attention, the progress on weakly coordinating and inert solvents almost stagnated. Here we study the effect of strategic F-substitution on the solvent properties of fluorobenzenes C6FxH6−x (xFB, x = 1–5). Asymmetric fluorination leads to dielectric constants as high as 22.1 for 3FB that exceeds acetone (20.7). Combined with the WCAs [Al(ORF)4]− or [(FRO)3Al-F-Al(ORF)3]− (RF = C(CF3)3), the xFB solvents push the potentials of Ag+ and NO+ ions to +1.50/+1.52 V vs. Fc+/Fc. The xFB/WCA-system has electrochemical xFB stability windows that exceed 5 V for all xFBs with positive upper limits between +1.82 V (1FB) and +2.67 V (5FB) vs. Fc+/Fc. High-level ab initio calculations with inclusion of solvation energies show that these high potentials result from weak interactions of the ions with solvent and counterion. To access the available positive xFB potential range with stable reagents, the innocent deelectronator salts [anthraceneF]+∙[WCA]− and [phenanthreneF]+∙[WCA]− with potentials of +1.47 and +1.89 V vs. Fc+/Fc are introduced.

From Coordination to Noncoordination: Syntheses and Substitution Lability Studies of Titanium Triflato Complexes.

A new concept for obtaining cationic complexes with triflate counteranions from coordinating triflato ligands was developed. Various routes are leading to titanium(IV) and titanium(III) triflato complexes efficiently. The reactions of pentafulvene titanium complexes with either triflic acid or silver triflate give the corresponding titanium(IV) triflato complexes in excellent yields. Hydrolysis of the titanium(IV) bistriflato complexes leads to cationic aqua complexes via displacement of the triflato ligand, which consequently acts as a noncoordinating anion. A functionalized titanium(IV) monotriflato complex was synthesized by insertion of a nitrile into the Ti-C bond and the triflato ligand was displaced by an NHC. While the titanium(IV) complexes are mostly inert toward substrates, the donor-free titanium(III) triflato complex is a strong Lewis acid and forms various adducts with monodentate Lewis bases. The titanium(III) complex was oxidized by reaction with TEMPO, resulting in a diamagnetic titanium(IV) complex. The reaction with bidentate ligands results in cationic titanium(III) complexes due to displacement of the triflato ligand by the bidentate ligands. Treatment with acetone leads to an aldol reaction of two acetone molecules and the formation of a cationic diacetone alcohol complex.

Fluorination/Dearomatization of C6F5 Groups: An FLP Route to an Electrophilic Borane and Non-Coordinating Anions.

B(C6F5)3 and the corresponding anion [B(C6F5)4]- are ubiquitous in main group and transition metal chemistry. Known derivatives are generally limited to the incorporation of electron donating substituents. Herein we describe electrophilic fluorination and dearomatization of such species using XeF2 in the presence of BF3 or Lewis acidic cations. In this fashion the anions [HB(C6F5)3]-, [B(C6F5)4]- and [(C6F5)3BC≡NB(C6F5)3]-, are converted to [FB(C6F7)3]-, [B(C6F7)4]-, and [(C6F7)3BC≡NB(C6F7)3]-, respectively. Similarly, the borane adducts (L)B(C6F7)3 (L=MeCN, OPEt3) are produced. These rare examples of electrophilic attack of electron deficient rings proceed as [XeF][BF4] acts as a frustrated Lewis pair effecting fluorination and dearomatization of C6F5 rings.

Carbon-Based Weakly Coordinating Anions: Molecular Design, Synthesis and Applications.

Although carbanions, which are usually regarded as reactive species and powerful metalation reagents, can be stabilized through choice of the substitution pattern, they have rarely been considered for the design of weakly coordinating anions (WCA). Here, we report on an evaluation of the potential of a series of differently substituted carbanions to serve as WCA by computational methods. This led us to the synthesis of the water- and air-stable allyl anion 1 with triflyl and 3,5-bis(trifluoromethyl)phenyl (ArF) moieties, which can be isolated in high yields even on a gram-scale. Single crystal X-ray crystallography and NMR studies confirmed the weak coordination ability of the anion by showing negligible or only weak interactions with different cations. This property enabled the application of 1 in the stabilization of reactive group 14 and 15 cations. In addition to the crystallization of a phosphenium cation, the first all-carbon salt with a non-aromatic carbanion is reported, which revealed to be a convenient reagent for hydride abstraction such as from silanes. Overall, this work demonstrates the so far untapped potential of carbanions as WCA, that are accessible with a variety of different cations for various applications.

Controlling Ionic Conductivity in Organometallic Ionic Liquids through Light-Induced Coordination Polymer Formation and Thermal Reversion.

Owing to their high ionic conductivity and negligible vapor pressure, ionic liquids (ILs) find applications in various electronic devices. However, fabricating IL-based photocontrollable devices remains a challenge. In this study, we developed organometallic ILs with reversible light- and heat-controlled ionic conductivities for potential use in tunable devices. The physical properties and stimulus responses of ILs containing a cationic sandwich Ru complex with two coordinating substituents were investigated. UV photoirradiation of these ILs triggered cation photodissociation, resulting in their transformation into viscoelastic coordination polymers wherein the coordinating substituents bridged the Ru centers. Owing to the anion coordination, salts with coordinating anions such as CF3SO2NCN-, B(CN)4-, and BF2(CN)2- exhibited faster response and higher conversion than those with noncoordinating anions including (FSO2)2N- and (CF3SO2)2N-. All photoproducts reverted to their original ILs upon heating, except for the photoproduct of the BF2(CN)2 salt, which decomposed upon heating. Light- and heat-induced reversible changes occur in most cases between the high-ionic-conductive IL state and low-ionic-conductive coordination polymer state. Unlike previously reported ILs with three or one cation substituent, the current ILs exhibited both high reactivity and large ionic conductivity changes.

Synthetic and Structural Peculiarities of Neutral and Cationic Molybdenum Imido and Tungsten Oxo Alkylidene Complexes Bearing Weakly Coordinating N‐Heterocyclic Carbenes

AbstractThe syntheses of the neutral molybdenum imido alkylidene N‐heterocyclic carbene (NHC) complexes of the general formula [Mo(NAr)(CHCMe2Ph)(NHC)XY] (Ar=2‐tBu‐C6H4, 2‐CF3‐C6H4, 2,6‐Me2‐C6H3, 2,6‐Cl2‐C6H3, adamantyl; X, Y=OTf, OC(CF3)3, OCH(CF3)2, OC6F5, SC6F5, 2,5‐bis(pentafluorophenyl)phen‐1‐yl) bearing electron‐withdrawing NHCs (1,3‐dimethyl‐4,5‐dichloroimidazol‐2‐ylidene (IMeCl2), 1,3,4‐triphenyl‐1,2,4‐triazol‐5‐ylidene (TPT)) are reported. Complementary, the corresponding cationic molybdenum imido alkylidene NHC complexes of the general formula [Mo(NAr)(CHCMe2R)(NHC)X+][B(ArF)4−/Al(OC(CF3)3)4−] (R=Me, Ph; B(ArF)4−=tetrakis (3,5‐bis(trifluoromethyl)phenyl)borate) have been prepared. Aiming at tungsten oxo complexes, reaction of [W(O)Cl2(CHCMe2Ph)(PMe2Ph)2] with [1,3‐dimethyl‐4,5‐dichloroimidazol‐2‐ylidene⋅AgI] (IMeCl2⋅AgI) followed by the addition of lithium terphenoxide yields [W(O)(CHCMe2Ph)(IMeCl2)(DPPO)2]. For comparison, [W(O)Cl(CHCMe2Ph)(IMes)(OSi(OtBu)3)] was prepared via reaction of [W(O)Cl2(CHCMe2Ph)(PMe2Ph)(IMes)] with KOSi(OtBu)3. [W(O)(CHCMe2Ph)(IMeCl2)(DPPO)(Et2O)+][B(ArF)4−] (DPPO=2,6‐diphenylphenoxide) became accessible via reaction of [W(O)(DPPO)2(CHCMe2Ph)(IMeCl2)] with anilinium B(ArF)4−. The structural peculiarities of selected complexes are reported. Benchmark ring‐closing metathesis and homometathesis reactions revealed that the neutral complexes bearing weakly coordinating NHCs such as IMeCl2 and TPT possessed only moderate activity, which could, however, be improved by preparing the corresponding cationic metal alkylidene complexes.

Atomistic molecular dynamics simulation and COSMO-SAC approach for enhanced 1,3-propanediol extraction with imidazolium-based ionic liquids.

1,3-Propanediol (1,3-PDO) is a key chemical in various industries, including pharmaceuticals and material sciences, and is projected to see significant market growth. However, the current challenges in its downstream processing, particularly in terms of cost and efficiency, highlight the need for innovative solutions. Our study delves into using ionic liquids (ILs) as a potential alternative, aiming to address these critical separation challenges more sustainably and efficiently. In this study, we utilized molecular dynamics (MD) simulations and the COSMO-SAC to examine 1,3-propanediol (1,3-PDO) extraction using four imidazolium-based ionic liquids with 1-butyl-3-methylimidazolium [Bmim] cation and with different anions bis(pentafluoroethanesulfonyl)imide [NPF2]-, bis(trifluoromethylsulfonyl)imide [NTF2]-, thiocyanate [SCN]-, and trifluoromethanesulfonate [TFO]-. Molecular dynamics simulations, incorporating analysis of radial distribution functions (RDF) and spatial distribution functions (SDF), revealed that [Bmim][SCN] and [Bmim][TFO] exhibit enhanced interactions with 1,3-PDO. Notably, [Bmim][SCN] formed the most hydrogen bonds, averaging 1.639 per molecule, due to its coordinating [SCN]- anion. This was in contrast to the fewer hydrogen bonds formed by non-coordinating anions in [Bmim][NPF2] and [Bmim][NTF2]. In ternary systems, [Bmim][SCN] and [Bmim][TFO] demonstrated superior selectivity for 1,3-PDO extraction compared to the other ionic liquids, with selectivity values around 29. These findings, supported by COSMO-SAC predictive modeling, highlight the potential of [Bmim][SCN] as a promising candidate for 1,3-PDO extraction, emphasizing the importance of anion selection in optimizing ionic liquid properties for this application. In our study, we employed MD simulations, incorporating the OPLS-AA force field, and COSMO-SAC to investigate the extraction of 1,3-PDO using imidazolium-based ionic liquids: [Bmim][NTF2], [Bmim][NPF2], [Bmim][SCN], and [Bmim][TFO]. The MD simulations were conducted using LAMMPS software, focusing on elucidating the RDF, SDF, and hydrogen bonding. Analysis of the distribution coefficient (β) and selectivity (S) for the ternary mixture was also conducted. These aspects of the simulation were analyzed using TRAVIS and VMD software. Additionally, the COSMO-SAC model was employed to determine the activity coefficients of 1,3-PDO in the ionic liquids, with molecular optimization conducted using Gaussian16 and sigma profile calculations performed using COSMO-SAC.

Design Principles and Routes for Calcium Alkoxyaluminate Electrolytes.

Multivalent-ion battery technologies are increasingly attractive options for meeting diverse energy storage needs. Calcium ion batteries (CIB) are particularly appealing candidates for their earthly abundance, high theoretical volumetric energy density, and relative safety advantages. At present, only a few Ca-ion electrolyte systems are reported to reversibly plate at room temperature: for example, aluminates and borates, including Ca[TPFA]2, where [TPFA]- = [Al(OC(CF3)3)4]- and Ca[B(hfip)4]2, [B(hfip)4]2- = [B(OCH(CF3)2)4]-. Analyzing the structure of these salts reveals a common theme: the prevalent use of a weakly coordinating anion (WCA) consisting of a tetracoordinate aluminum/boron (Al/B) center with fluorinated alkoxides. Leveraging the concept of theory-aided design, we report an innovative, one-pot synthesis of two new calcium-ion electrolyte salts (Ca[Al(tftb)4]2, Ca[Al(hftb)4]2) and two reported salts (Ca[Al(hfip)4]2 and Ca[TPFA]2) where hfip = (-OCH(CF3)2), tftb = (-OC(CF3)(Me)2), hftb = (-OC(CF3)2(Me)), [TPFA]- = [Al(OC(CF3)3)4]-. We also reveal the dependence of Coulombic efficiency on their inherent propensity for cation-anion coordination.

Synthesis of Superbulky Amide Ligands by Addition of Polar Reagents to Sila-Imine.

The chemistry of extremely bulky amide ligands is troubled by difficulties in deprotonation of the parent amine. As an alternative route to superbulky amide reagents, the addition of polar reagents to a sila-imine has been investigated. Attempts to synthesize the superbulky amide anion (tBu3Si)2N- by addition of tBuLi to tBu2Si=N(SitBu3) failed and gave tBu3Si(tBu2HSi)NLi and isobutene. Reaction of the sila-imine with KOtBu successfully led to tBu3Si[tBu2(tBuO)Si]NK which crystallized as a separated ion-pair. Reaction with the slightly bulkier KOAd (Ad=1-adamantyl) led in presence of THF to ether ring-opening. Reaction with tBuOH gave tBu3Si[tBu2(tBuO)Si]NH but this amine cannot be easily deprotonated. Reaction with (BDI*)MgnBu in presence of THF gave (BDI*)Mg+ ⋅ (THF)2 and the non-coordinating anion tBu3Si[tBu2(nBu)Si]N-; BDI*=ß-diketiminate ligand HC[C(tBu)N-DIPP]2, DIPP=2,6-diisopropylphenyl. Reaction of Mg(nBu)2 with tBu2Si=N(SitBu3) led to a Mg complex with one amide ligand: tBu3Si[tBu2(nBu)Si]N-. The other superbulky amide anion isomerized by internal deprotonation of a tBu-substituent to give a primary carbanion that is also coordinated to Mg. Although the amide-to-carbanion isomerization is highly contrathermodynamic, it allows for coordination of both anions to a single Mg center. The new bulky amides are rare cases of halogen-free weakly coordinating anions.

Ionic Liquid Crystals Based on Loop-Shaped Copper(I) Complexes.

This paper describes the synthesis and characterization of liquid crystals based on loop-shaped cationic copper(I) complexes of a multidentate ligand. Their synthesis involves the one-pot reaction of an alkyloxy-decorated pyridine-aldehyde unit with a diamine (2,2'-(ethylenedioxy)bis(ethylamine)) spacer to form in situ a pyridine-imine quadridentate-N4-donor ligand, L, which is able to chelate a copper(I) center associated with various noncoordinating anions. All of these compounds were characterized by NMR, IR, and electronic absorption spectroscopy, and more particularly by X-ray diffraction and mass spectroscopy, enabling unambiguous assignment of the [ML]+ mononuclear nature of the cationic components. The presence of six flexible alkyloxy chains at each end of the ligand associated with the rigidity of the core complex causes induction of a liquid crystal state with a columnar self-organized architecture, where the columns are packed in a hexagonal two-dimensional network.

Biorelevant Weakly Coordinating Directing Group Assisted C-H Alkenylation with Cyclopropanols via Sequential C-H/C-C Activation.

A weakly coordinating biorelevant intrinsic directing group (DG) assisted site-selective C-H alkenylation via sequential C-H/C-C bond activation has been accomplished under Ru(II)-catalysis using readily accessible cyclopropyl alcohol as an alkenyl surrogate. Utilization of an intrinsic DG, exclusive regioselectivity, functional group diversity, late-stage natural product and drug mutations are the important practical features.

Asymmetric hydrogenation of isoquinolines with chiral cationic ruthenium diamine catalysts

A general asymmetric hydrogenation of isoquinolines catalyzed by chiral cationic ruthenium catalysts has been investigated. A wide range of isoquinoline derivatives, including 1-substituted, 3-substituted, 1,3-disubstituted and 3,4-disubstituted isoquinolines, were efficiently hydrogenated to give chiral tetrahydroisoquinolines with up to 92 % ee and >20:1 dr. It was found that the ruthenium catalyst bearing a non-coordinating BArF anion resulted in high enantioselectivity. Preliminary mechanistic studies revealed that the isoquinoline is reduced via a stepwise pathway, including 1,2-hydride addition, isomerization, and 2,3-hydride addition.

Photoluminescence of Mn2+ in the Borosulfate Zn[B2(SO4)4]:Mn2+ - A Tool to Detect Weak Coordination Behavior of Ligands.

The impact of the surrounding ligand field is successfully exploited in the case of Eu2+ to tune the emission characteristics of inorganic photoactive materials with potential application in e.g., phosphor-converted white light-emitting diodes (pc-wLEDs). However, the photoluminescence of Mn2+ related to intraconfigurational 3d5-3d5 transitions is also strongly dependent on local ligand field effects and has been underestimated in this regard so far. In this work, we want to revive the idea how to electronically tune the emission color of a transition metal ion in inorganic hosts by unusual electronic effects in the metal-ligand bond. The concept is explicitly demonstrated for the weakly coordinating layer-like borosulfate ligand in the Mn(II)-containing solid solutions Zn1-xMnx[B2(SO4)4] (x = 0, 0.03, 0.04, 0.05, 0.10). Zn[B2(SO4)4]:Mn2+ shows orange narrow-band luminescence at 590 nm, which is an unusually short wavelength for octahedrally coordinated Mn2+ and indicates an uncommonly weak ligand field. On the other hand, the analysis of the interelectronic Racah repulsion parameters reveals ionic Mn-O bonds with values close to the Racah parameters of the free Mn2+ ion. Overall, this strategy demonstrates that electronic control of the metal-ligand bond can be a tool to make Mn2+ a potent alternative emitter to Eu2+ for inorganic phosphors.

Toughening self-healing elastomer crosslinked by metal–ligand coordination through mixed counter anion dynamics

Mechanically tough and self-healable polymeric materials have found widespread applications in a sustainable future. However, coherent strategies for mechanically tough self-healing polymers are still lacking due to a trade-off relationship between mechanical robustness and viscoelasticity. Here, we disclose a toughening strategy for self-healing elastomers crosslinked by metal–ligand coordination. Emphasis was placed on the effects of counter anions on the dynamic mechanical behaviors of polymer networks. As the coordinating ability of the counter anion increases, the binding of the anion leads to slower dynamics, thus limiting the stretchability and increasing the stiffness. Additionally, multimodal anions that can have diverse coordination modes provide unexpected dynamicity. By simply mixing multimodal and non-coordinating anions, we found a significant synergistic effect on mechanical toughness ( > 3 fold) and self-healing efficiency, which provides new insights into the design of coordination-based tough self-healing polymers.

Interpenetration Phenomena via Anion Template Effects in Fe(II) and Co(II) Coordination Networks with a Bis-(1,2,4-triazole) Ligand.

Seven new coordination networks, [Fe(tbbt)3](BF4)2 (1), [Co(tbbt)3](BF4)2 (2), [Fe(tbbt)3](ClO4)2 (3), [Co(tbbt)3](ClO4)2 (4), [Fe(NCS)2(tbbt)2] (5), [Co(NCS)2(tbbt)2] (6), and [Fe(H2O)2(tbbt)2]Br2·2H2O (7), were synthesized with the linker 1,1'-(trans-2-butene-1,4-diyl)bis-1,2,4-triazole (tbbt) and structurally investigated. The structure of complexes 1-4 is composed of three interpenetrating, symmetry-related 3D networks. Each individual 3D network forms a primitive, nearly cubic lattice (pcu) with BF4- or ClO4- anions present in the interstitial spaces. The structure of compounds 5 and 6 is composed of two-dimensional sql layers, which are parallel to each other in the AB stacking type. These layers are interpenetrated by one-dimensional chains, both having the same formula unit, [M(NCS)2(tbbt)2] (M = Fe, Co). The structure of compound 7 consists of parallel, two-dimensional sql layers in the ABCD stacking type. The interpenetration in 1-6 is not controlled by π-π-interactions between the triazole rings or C=C bonds, as could have been expected, but by (triazole)C-H⋯F4B, C-H⋯O4Cl, and C-H⋯SCN anion hydrogen bonds, which suggests a template effect of the respective non-coordinated or coordinated anion for the interpenetration. In 7, the (triazole)C-H⋯Br anion interactions are supplemented by O-H⋯O and O-H⋯Br hydrogen bonds involving the aqua ligand and crystal water molecules. It is evident that the coordinated and non-coordinated anions play an essential role in the formation of the networks and guide the interpenetration. All iron(II) coordination networks are colorless, off-white to yellow-orange, and have the metal ions in the high-spin state down to 77 K. Compound 5 stays in the high spin state even at temperatures down to 10 K.

Impact of counter anions on structural and magnetic properties of iron(III) meso-tetraphenylporphyrin tetrahydrofurane solvates

Intensively researched iron meso-tetraphenylporphyrin (FeTPP) complexes are central to the functionalities of many biological systems while at the same time they possess intriguing magnetic properties. Here we report on the synthesis and structural characterization of FeTPP complexes with axial tetrahydrofuran (THF) ligand and different non-coordinating counter anions. Structurally, the most interesting feature of these complexes is the stretching of the distance between the iron(III) and the oxygen atom of the THF ligand for different counter anions. This parameter affects the magnetic anisotropy of FeTPP as studied here with magnetic susceptibility, χm, and X-band electron paramagnetic resonance (EPR). Both magnetic probes are consistent with the iron(III) in its high-field state S = 5/2. Simulations of temperature dependencies of χm and EPR spectra show that the zero-field splitting magnetic anisotropy parameter D decreases with the tetragonal elongation of the hexa-coordinated iron(III) geometry, which is qualitatively discussed within the ligand field theory.

Synthesis of novel NHC-based transition metal complexes of Pd(II), Au(I), Cu(I) and Ir(III) with pendant 1,2,3-triazole group for remediation of rhodamine B

The transition metal-NHC complexes presented here were all created by us. For instance, A bidentate ligand, [L1-H(Br)] having 1-methyl imidazolium salt, using for N-heterocyclic carbene as precursor, connected to a pendant triazole moiety via methylene bridge has been synthesized via ‘CuAAC’ or ‘Click’ reaction. Imidazolium salt, [L1-H(PF6)] with a non-coordinating anion PF6 has been prepared via anion exchange of [L1-H(Br)] with NH4PF6. Reaction of [L1-H(PF6)] with half an equivalent of Ag2O yielded the Ag(I)–NHC complex [(L1)2Ag](PF6). This Ag(I)–NHC complex is shown to be an excellent carbene transfer agent to other transition metals, both linear and non-linear, when reacted with appropriate equivalents of metal precursors to give variety of organometallic metal-NHC complexes via transmetallation. The compound [(L1)IrCl(Cp*)](PF6) has been applied for the remediation of a water pollutant rhodamine B dye from wastewater. The results of this study also provide good opportunities for organic synthesis in future research.