Cyclometallated Ring Research Articles

Rhodium-catalyzed selective direct arylation of phosphines with aryl bromides

The widespread use of phosphine ligand libraries is frequently hampered by the challenges associated with their modular preparation. Here, we report a protocol that appends arenes to arylphosphines to access a series of biaryl monophosphines via rhodium-catalyzed P(III)-directed ortho C–H activation, enabling unprecedented one-fold, two-fold, and three-fold direct arylation. Our experimental and theoretical findings reveal a mechanism involving oxidative addition of aryl bromides to the Rh catalyst, further ortho C–H metalation via a four-membered cyclometalated ring. Given the ready availability of substrates, our approach opens the door to developing more general methods for the construction of phosphine ligands.

The function of Chalcogenophene in the Cyclomatelated Ring of the Cycloruthenated Dyes applied in Dye-Sensitized Solar Cell.

Three thiocyanate-free cycloruthenated complexes, DUY24-O, DUY24, and DUY24-Se containing furan, thiophene, and selenophene, respectively, as a part of the cycloruthenated ring, were designed to reveal the function of the chalcogen atom on the physicochemical and photovoltaic performance of the cycloruthenated sensitizers applied in dye-sensitized solar cells (DSCs). The three sensitizers have a similar molecular size; therefore, the effect of molecular dimensions on their photovoltaic performance can be negligible. NMR data, electron-donating resonance effects, optical properties, and the energy levels of the frontier orbitals reveal that the physical/photovoltaic properties of the three sensitizers were affected significantly by the chalcogen atom on the cyclometalated chalcogenophene ring. The λmax (both in ethanol and adsorbed on TiO2), frontier orbital level, and dye loading of thiophene- and selenophene-containing dyes are very close. Nevertheless, DUY24-Se has a higher molar absorption coefficient compared to DUY24; therefore, the DSC based on DUY24-Se has higher efficiency (8.4% under AM1.5 G one-sun and 26% under T5-light at ca. 6000 lux) than that sensitized with the DUY24 dye. These efficiencies are also higher than those (7.9 and 21.6%, respectively) of the cell dyed with N719, fabricated using the same conditions. The better performance of the device sensitized with DUY24-Se compared to DUY24-based cells suggests that selenophene is as good as (or even better than) thiophene to be a part of the cyclometalated ring for thiocyanate-free cycloruthenated sensitizers applied in DSCs. Furan-containing DUY24-O has much worse photovoltaic performance compared to the other two dyes. This is not only because DUY24-O has the shortest λmax, the lowest molar absorption coefficient, and the highest HOMO level but also the lowest dye loading (because of the strong interaction between the oxygen in furan and TiO2, the array of DUY24-O occupies more surface when adsorbed on TiO2) and the fastest charge recombination. The physicochemical and photovoltaic properties as well as the adsorption behavior of the dye on the TiO2 anode for the cycloruthenated sensitizers affected significantly by the chalcogen atom of the chalcogenophene on the cyclometalated ring provide a new strategy to design high-efficiency NCS-free cyclometalated sensitizers for DSCs.

Synthetic and Structural Study on Orthometallated Ferrocene Complexes: Non‐Planar Metallabenzene and Five‐Membered Metallacycle Complexes with Closed Os3 Triangles

Thermolysis of (Z)‐1‐ferrocenyltelluro‐1‐ferrocenyl‐4‐ferrocenyl‐1‐buten‐3‐yne with [Os3(CO)12] in toluene gave two new clusters: non‐planar six‐membered metallacycle complex [Os3H(CO)7(µ3‐Te){η1:η1:η2:η2‐FcCCC(H)(Fc)2}] (1, Fc = ferrocenyl) and five‐membered cyclometallated ring complex [Os3(CO)7(µ3‐Te){η1:η1:η3‐FcC(H)C(H)CC(Fc)2}] (2). Compounds 1 and 2 may be thought to form by orthometallation of ferrocene with a closed Os3 triangle by intramolecular rearrangement of atoms within the cluster complexes. Typically the formation of a non‐planar metallabenzene such as 1 may involve the orthometallation of another aromatic ring. Also, conversion of 1 to 2 shows the initial step required for alkene hydrogenation by a tellurium‐bridged triosmium cluster. Both compounds were characterized by IR and 1H NMR spectroscopy, and their structures established by single‐crystal XRD.

Phosphorescent Iridium(III) Complexes of Cyclometalated 5-Aryl-1H-1,2,4-Triazole Ligands: Structural, Computational, Spectroscopic, and Device Studies

Ir(III) complexes of cyclometalated 5-aryl-1H-1,2,4-triazole ligands are highly efficient, phosphorescent emitters. We describe herein a series of fac-IrL3 complexes, in which the nature of aryl substituents are shown to strongly affect emission wavelength over the range 453–499 nm. Computational and structural studies indicate that for aryl groups the point of attachment and dihedral angle with respect to the cyclometalated ring influence emission color. Significantly, this degree of color tuning may be achieved without resorting to electron-withdrawing or -donating groups. Photo- and electroluminescence device studies of the different emitters indicate that they are generally highly efficient: photoluminescent efficiencies >90% and external quantum efficiencies of up to 22% are observed.

Cyclometalated Complexes of Platinum(II) with 2‐Vinylpyridine

AbstractThe electron‐rich platinum(II) derivatives [Pt(R)2(DMSO)2] (R = Me, Ph) react with 2‐vinylpyridine (L) to give the cyclometalated complexes [Pt(L–H)(R)(DMSO)] through C–H bond activation. Cyclometalation also occurs with [Pt(Me)(Cl)(DMSO)2]. From the starting compounds, a series of cyclometalated complexes was obtained and characterised by analytical and spectroscopic methods. The molecular structures of [Pt(L–H)(Me)(PPh3)] and [Pt(L–H)(Ph)(PCy3)] were solved by X‐ray diffraction analysis, and the results unambiguously demonstrate cyclometalation of 2‐vinylpyridine. The five‐membered cyclometalated ring is particularly stable, likely due to partial electronic delocalisation.

Red emitting [Ir(C^N)2(N^N)]+complexes employing bidentate 2,2′:6′,2′′-terpyridine ligands for light-emitting electrochemical cells

2,2':6',2''-Terpyridine (tpy), 4'-(4-HOC6H4)-2,2':6',2''-terpyridine (1), 4'-(4-MeOC6H4)-2,2':6',2''-terpyridine (2), 4'-(4-MeSC6H4)-2,2':6',2''-terpyridine (3), 4'-(4-H2NC6H4)-2,2':6',2''-terpyridine (4) and 4'-(4-pyridyl)-2,2':6',2''-terpyridine (4) act as N^N chelates in complexes of the type [Ir(C^N)2(N^N)][PF6] in which the cyclometallating ligand, C^N, is derived from 2-phenylpyridine (Hppy) or 3,5-dimethyl-1-phenyl-1H-pyrazole (Hdmppz). The single crystal structures of eight complexes have been determined, and in each iridium(III) complex cation, the non-coordinated pyridine ring of the tpy unit is involved in a face-to-face π-stacking interaction with the cyclometallated ring of an adjacent ligand. Solution NMR spectra of the [Ir(ppy)2(N^N)](+) complexes are consistent with the presence of a non-classical hydrogen bond between the non-coordinated N-donor of the tpy domain and a CH unit of one pyridine ring of an adjacent ppy(-) ligand; the presence of the N···HC interaction was confirmed in one of the solid-state structures. The pendant pyridine ring of the coordinated tpy undergoes hindered rotation on the NMR timescale at 295 K. In CH2Cl2, the complexes are orange or red emitters, with λ(max)(em) in the range 580 to 642 nm; photoluminescence quantum yields (PLQY) are <10%, and lifetimes range from 54 to 136 ns. N-Methylation of the pendant 4'-(4-pyridyl) group in [Ir(dmppz)2(pytpy)][PF6] essentially quenches the emission. Light-emitting electrochemical cells (LECs) have been fabricated in a thin film configuration; the emission spectra of the LECs are red-shifted with respect to the PL spectra of the corresponding complex in thin film configuration. For the device incorporating [Ir(ppy)2(pytpy)][PF6], the PL to EL red-shift is extremely large and this is indicative of a different emitting state being involved. The most efficient devices used [Ir(ppy)2(1)][PF6], [Ir(ppy)2(2)][PF6] or [Ir(ppy)2(3)][PF6] in the emissive layer; the devices exhibited rapid turn-on times, but showed relatively low efficiencies in accordance with the solid state photoluminescence quantum yields.

Synthesis, Characterization, and Fluxional Behavior of a 34 Electron Homochiral Dimetallic Complex with an Unsupported Hydride Bridge between Two Ru Atoms

The binuclear η6-benzene cycloruthenated complex 2, which bears an unsupported bridging hydride ligand, was synthesized by treating the monomeric cationic cycloruthenated (R)-(+)-1-(1-naphthyl)ethylamine 1 with potassium hydroxide under biphasic conditions and then with an alcoholic solvent. Alternatively, compound 2 was prepared from an equimolar amount of compound 1 and the homologous monomeric hydrido complex 3. The crystal structure of 2 revealed π-stacking interactions between the naphthyl groups of each cyclometalated amine; the hydride ligand is bent, with a Ru–H–Ru angle of 145.3(10)°. Compound 2 is fluxional as shown by variable-temperature NMR analysis. DFT analysis of homochiral 2 and of its hypothetical heterochiral counterpart 2* revealed that dispersion-based π–π interactions between the cyclometalated ring are not the only interactions that must be taken into account to rationalize the conformational preference for 2. Indeed, the overall dispersion-based interactions between all the ligands of the connected metallacycles provide an additional 5 to 6 kcal/mol of stabilization energy for 2 regardless whether the π-stacking interactions between the naphthyl rings exist or not.

Self-assembly of cyclometallated Pd(II) compounds directed by C–H⋅⋅⋅π interactions: A structural evidence for metalloaromaticity in a cyclopalladated ring

Structural studies on the two binuclear cyclometallated compounds [Pd(C2,N-bzan)(μ-N3)]2 (1) and [Pd(C2,N-bzan)(μ-Pz)]2 (2) (bzan = N-benzylideneaniline) have been carried out in this work. In both compounds, C–H⋅⋅⋅π interactions play an important role in the molecular self-assembly. In complex 1, ortho-CH bonds from bzan moiety interact with the cyclopalladated ring at a distance of Cbzan⋅⋅⋅Cg 3.448(6) Å, providing a new structural evidence for the metalloaromaticity of the cyclometallated ring.

One-step formation of cyclometallated Au(III) N,S-heterocyclic carbene: crystallographic analysis

Gold(I) N,S-heterocyclic carbene AuBr(NSHC) (NSHC = N-allylbenzothiazolin-2-ylidene) (1) with an allyl pendant is oxidised by iodine to give [AuI2(NSHC)2]+[I3]- (2) and a cyclometallated byproduct AuBr2(-C6H4SCNCH2CHCH2Br-C,C) (3). The latter can be prepared directly from bromination of 1. Similar reaction with the crotyl (but-2-en-1-yl) derivative AuBr(NSHC) (NSHC = N-crotylbenzothiazolin-2-ylidene) (4) gives an oxidative addition product AuBr3(C6H4SCNCH2CHCHCH3) (5). X-Ray single-crystal crystallographic analysis of 3 reveals a 5-membered cyclometallated ring in a sq planar metal that gives two types of AuIII-C bonds. Similar structural analysis has also been carried out in 1, 2 and 5.

Mechanism of the Competition between Phenyl Insertion and Ligand Reductive Elimination on a Hindered Platinum(IV) Cyclometalated Complex

Careful tuning of the reaction conditions has been proved to be essential for the operation of two disjunctive reaction mechanisms occurring on the ortho-metalated platinum compounds [PtIVBr(Ph)2(C5CH4CHNZ)(SMe2)] (Z = Me, Bzl, CH2(2,4,6-Me3C6H2)). In dilute solutions, where the already established lability of the SMe2 ligand favors the existence of the pentacoordinated {PtIVBr(Ph)2(C4CH4CHNZ)} species, the complex evolves to produce the insertion of one of the phenyl ligands into the cyclometalated PtIV−C bond to yield the complexes [PtIIBr(C4CH3C6H4CHNZ)(SMe2)], which contain a seven-membered cyclometalated ring. The process involves the formation of an hydride intermediate, which has been detected via low-temperature proton NMR for Z = Bzl, prior to the reductive elimination of benzene. In more concentrated solutions, or in the presence of large amounts (200−500 fold) of SMe2, the existence of pentacoordinated species is reduced to a minimum and a reductive C−C coupling takes place between the metalated imine carbon and one of the phenyl ligands, yielding the coordination complexes [PtIIBr(Ph)(C6H3C6H4CHNZ)(SMe2)], which evolve rapidly to trans-[PtIIBr(Ph)(SMe2)2] and free C5H3C6H4CHNZ. The validity of the mechanisms proposed has been proved via stoichiometric and reactivity studies carried out under carefully controlled conditions, both on initial PtIV complex and on the final inserted complex, [PtIIBr(C4CH3C6H4CHNZ)(SMe2)]. The overall reactivity is rather surprising, given the generally accepted dissociative processes involved in the preliminary steps of reductive elimination reactions on PtIV complexes. DFT calculations have been carried out in order to check the energetic validity of the proposed disjunctive reaction mechanisms. From the data obtained, it is clear that the formation of the pentacoordinated species {PtIVBr(Ph)2(C5CH4CHNZ)} could effectively lead to the standard C−C reductive coupling, but in our case the existence of the parallel insertion process is highly favored. As a consequence the observed reductive elimination reaction can only occur via the otherwise less favored direct C−C coupling on the octahedral [PtIVBr(Ph)2(C4CH4CHNZ)(SMe2)] starting material.

Triruthenium, Hexaruthenium, and Triosmium Carbonyl Derivatives of 2-Amino-6-phenylpyridine

The triruthenium cluster complexes [Ru3(I-H)(I3- 2 -HapyPh-N,N)(CO)9 ]( 1) and [Ru3(I‚)2(I3- 3 -HapyC6H4-N,N,C)2(CO)6 ]( 2) and the hexaruthenium ones [Ru6(I3-H)2(I5- 2 -apyPhN,N)(I-CO)2(CO)14 ]( 3) and [Ru6(I3-H)(I5- 3 -apyC6H4-N,N,C)(I-CO)3(CO)13 ]( 4) have been prepared from [Ru3(CO)12] and 2-amino-6-phenylpyridine (H2apyPh). Compound 1 contains a deprotonated HapyPh ligand capping a face of the metal triangle. Compound 2 contains two cyclometalated HapyC6H4 ligands, each spanning a Ru-Ru edge through the N atom of the amido fragment and chelating the remaining Ru atom through both the pyridine N atom and the C atom of the cyclometalated ring. The hexanuclear derivatives 3 and 4 have an uncommon basal edge-bridged square pyramidal metallic skeleton. The bridging ligand of 3 is a doubly deprotonated apyPh ligand which caps the metallic square through the exocyclic N atom, while is attached to the Ru atom that bridges the edge of the square pyramid through the pyridine N atom. Complex 4 is structurally related to 3 but has a cyclometalated phenyl ring. It has been established that compound 2 is formed by reaction of 1 with H2apyPh and that complex 3 is formed by reaction of 1 with [Ru3(CO)12]. While the hydrogenation of 4 gives 3, the thermolysis of 3 gives 4 among other unidentified products. The reaction of the osmium cluster [Os3(CO)10(MeCN)2] with H2apyPh gives a 1:5 mixture of the edge-bridged decacarbonyl derivatives [Os3(I-‚)(I- 1 -HapyPh-N)(CO)10 ]( 5) and [Os3(I-H)(I- 2 -HapyPhN,N)(CO)10 ]( 6). Both compounds give the face-capped nonacarbonyl derivative [Os3(I-H)(I3- 2 -HapyPh-N,N)(CO)9 ]( 7) upon irradiation with UV light. Curiously, while complexes 5 and 7 are stable in refluxing toluene, the thermolysis of 6 gives a mixture of 5, 7, and the cyclometalated dihydride [Os3(I-H)2(I- 3 -HapyC6H4-N,N,C)(CO)9 ]( 8).

Clivagem dos ciclopaladados diméricos [Pd(dmba)(m-X)]2 (dmba = N,N-dimetilbenzilamina; X = Cl, N3, NCO) por tiouréia

Ciclopaladados diméricos do tipo [Pd(dmba)(m-X)]2 (dmba = N,N-dimetilbenzilamina; X = Cl, N3, NCO) reagem com tiouréia (tu), à temperatura ambiente, resultando espécies mononucleares do tipo [Pd(dmba)(X)(tu)]. Todos os compostos foram caracterizados por análise elementar, espectroscopias no IV e de RMN de ¹H e com base nessas técnicas as estruturas, desses compostos, foram propostas. Os espectros de absorção no infravermelho mostraram que a coordenação da tiouréia, ao paládio, ocorre através do átomo de enxofre. O anel ciclometalado foi confirmado através da espectroscopia de RMN de ¹H.

Triruthenium and Triosmium Carbonyl Cluster Complexes Containing Bridging Ligands Derived from 2-Amino-7,8-benzoquinoline

The ruthenium cluster complexes [Ru 3 (μ 3 -η 3 -abq-C,N,N)(CO) 9 ] (1) and [Ru 3 (μ-H) 2 (μ 3 -η 3 -abq-C,N,N) 2 (CO) 6 ] (2) (H 2 abq = 2-amino-7,8-benzoquinoline) have been stepwise prepared from [Ru 3 (CO) 1 0 (MeCN) 2 ]. Both compounds contain cyclometalated abq ligands which span a Ru-Ru edge through the N atom of an amido fragment and chelate the remaining Ru atom through both the quinolinic N atom and the C atom of the cyclometalated ring. For steric reasons, the cyclometalation is responsible for the observation of short Ru-N a m i d o bond lengths. The reaction of the osmium cluster [Os 3 (CO) 1 0 (MeCN) 2 ] with H 2 -abq gives the amido-bridged decacarbonyl derivative [Os 3 (μ-H)(μ-η 1 -Habq-N)(CO) 1 0 ] (3). Curiously, while complex 3 is stable in refluxing toluene, the ruthenium analogue of 3 has not been detected. Compounds 1-3 represent the first trinuclear carbonyl clusters containing ligands derived from 2-amino-7,8-benzoquinoline.

Cyclometallated complexes of ruthenium and osmium containing the o-C 6H 4PPh 2 ligand

The reaction between [Hg( o-C 6H 4PPh 2) 2] and [MHCl(CO)(PPh 3) 3] gives the complexes [ MCl(o-C 6H 4P Ph 2)(CO)(PPh 3) 2] [M=Ru ( 1), Os ( 2)], which contain a four-membered cyclometallated ring. A single-crystal X-ray diffraction study of 2 shows the geometry about osmium to be distorted octahedral with the phosphorus atoms in a meridional arrangement. Both complexes react with CO, which displaces one of the triphenylphosphine ligands, the product from 2 being [ OsCl(o-C 6H 4P Ph 2)(CO) 2(PPh 3)]. In the case of 1, there is an accompanying migratory insertion of coordinated CO into the RuC bond to give the five-membered cyclic acyl complex [ RuCl(o-C(O)C 6H 4P Ph 2)(CO) 2(PPh 3)]. Complex 2 reacts with AgSbF 6 in the presence of CO to give [ Os(o-C 6H 4P Ph 2)(CO) 2(PPh 3) 2]SbF 6.

Synthesis and Second-Order Nonlinear Optical Properties of New Palladium(II) and Platinum(II) Schiff-Base Complexes

The second harmonic generations of the dimeric complexes [M2(μ-X)(μ-SCnH2n+1)(RC6H3CHNC6H4R‘)] (M = Pd, Pt; X = Cl, CH3COO, (R)-CH3CHClCOO; R, R‘ = NO2 and OC8H17 or N(C4H9)2; n = 4 or 8) and the monomeric complexes [Pd(RC6H3CHNC6H4R‘)L] (L = C5H5 (Cp), CH3COCHCOCH3 (acac)) and [Pd(RC6H3CHNC6H4R‘)(CNC6H4R‘‘)Cl] (R‘‘ = NO2, OCnH2n+1, N(CmH2m+1)2; n = 4 or 8; m = 1 or 4) have been measured, and the influence of the position of donor and acceptor groups is discussed and compared with that of the free imine ligands. The value of the hyperpolarizability (β) is raised only when a strong donor group is located in the cyclometalated ring. Moreover, the β value has been enhanced, too, in the cyclopentadienyl monomer complex by as much as 80% with respect to the β value of the corresponding free imine. The molecular structure of [Pd2(μ-Cl)(μ-SC4H9)(N(C4H9)2C6H3CHNC6H4NO2] has been determined by an X-ray diffraction analysis.

Six-membered cyclometallated derivatives of platinum(II) derived from 2-benzylpyridines. Crystal and molecular structure of [Pt(L)(Ph 3P)Cl] (HL = 2-(1-methylbenzyl)pyridine)

The reaction of K 2[PtCl 4] with 2-(1-methylbenzyl)pyridine, HL, and 2-benzylpyridine, HL', affords the cyclometallated species [{Pt(L)Cl} 2] ( 1) and [{Pt(L')Cl} 2] ( 2), respectively. The chloride bridge in complex 1 can be split by neutral or anionic species to give the monomeric, [Pt(L)(Ph 3P)Cl], as two isomers, trans-P-Pt-C ( 3) and trans-P-Pt-N, ( 4), [Pt(L)(py)Cl] ( 5), [Pt(L)(CO)Cl] ( 6), [Pt(L)(CNCH 2SO 2C 6H 4CH 3-4)Cl] ( 7), [Pt(L)(acac)] (Hacac = 2,4-pentanedione) ( 8), [Pt(L)(dppm)][BF 4] (dppm = bis(diphenyl-phosphino)methane) ( 9), [Pt(L)(dppe)][BF 4] (dppe = bis(diphenylphosphino)ethane) ( 10) and [Pt(L)(dipy)][BF 4](dipy = 2,2'-dipyridine) ( 11). Similarly, compound 2, by reaction with Ph 3P, affords [Pt(L')(Ph 3P)Cl], as two isomers, trans-P-Pt-C ( 12) and trans-P-Pt-N ( 13). Reaction of compounds 1 or 4 with AgBF 4 in acetonitrile affords [Pt(L)(CH 3CN) 2 IBF 4] ( 14) or [Pt(L)(Ph 3P)-(CH 3CN)][BF 4] ( 15). From these, [Pt(L)(Ph 3P) 2][BF 4] ( 16), [Pt(L)(Ph 3P)(CO)][BF 4] ( 17) and [Pt(L)(Ph 3P)(py)][BF 4] ( 18), can be obtained by displacement of the coordinated acetonitrile. The new complexes were characterized by IR, 1H and 31P NMR and FAB-MS spectroscopic techniques. The NMR spectra at room temperature of most of the species derived from HL give evidence for the presence in solution of two diastereomers a and b. The structure of one diastereomer of complex 4 has been solved by single crystal X-ray diffraction, 4b. The platinum atom is in an almost square planar geometry with a P-Pt-N trans arrangement: Pt-N = 2.095(3), Pt-C = 1.998(4), Pt-P = 2.226(1) and Pt-Cl = 2.400(1) Å. The six-membered cyclometallated ring is in a boat conformation, with the CH 3 group in an equatorial position, i.e pointing away from the metal. Attempts to obtain [{Pt(L″)Cl} 2] (HL″ = 2-(dimethylbenzyl)pyridine), afforded an insoluble product heavily contaminated by platinum metal; treatment of this crude material with Ph 3P gave [Pt(L″)(Ph 3P)Cl] ( 19).

Cyclometalated complexes of palladium(II) and platinum(II) with N-benzyl- and N-(phenylethyl)-.alpha.-benzoylbenzylideneamine. Delocalization in the cyclometalated ring as a driving force for the orthometalation

ADVERTISEMENT RETURN TO ISSUEPREVArticleNEXTCyclometalated complexes of palladium(II) and platinum(II) with N-benzyl- and N-(phenylethyl)-.alpha.-benzoylbenzylideneamine. Delocalization in the cyclometalated ring as a driving force for the orthometalationCarmen Navarro-Ranninger, Isabel Lopez-Solera, Amparo Alvarez-Valdes, Jesus H. Rodriguez-Ramos, Jose R. Masaguer, Jose L. Garcia-Ruano, and Xavier SolansCite this: Organometallics 1993, 12, 10, 4104–4111Publication Date (Print):October 1, 1993Publication History Published online1 May 2002Published inissue 1 October 1993https://doi.org/10.1021/om00034a052RIGHTS & PERMISSIONSArticle Views250Altmetric-Citations70LEARN ABOUT THESE METRICSArticle Views are the COUNTER-compliant sum of full text article downloads since November 2008 (both PDF and HTML) across all institutions and individuals. These metrics are regularly updated to reflect usage leading up to the last few days.Citations are the number of other articles citing this article, calculated by Crossref and updated daily. Find more information about Crossref citation counts.The Altmetric Attention Score is a quantitative measure of the attention that a research article has received online. Clicking on the donut icon will load a page at altmetric.com with additional details about the score and the social media presence for the given article. Find more information on the Altmetric Attention Score and how the score is calculated. Share Add toView InAdd Full Text with ReferenceAdd Description ExportRISCitationCitation and abstractCitation and referencesMore Options Share onFacebookTwitterWechatLinked InReddit PDF (946 KB) Get e-AlertsSupporting Info (1)»Supporting Information Supporting Information Get e-Alerts

Multiple chlorinations of the cyclometallated ring in iridium triaryl phosphite complexes: the crystal and molecular structure of [IrCl2{P(OC6Cl3Me-o)(OC6H4Me-o)2}(pyridine)(PMe3)

Complete aromatic substitution of cyclometallated aromatic rings in a series of iridium triaryl phosphite complexes is found to occur rapidly with Cl2 in benzene: the structure of [IrCl2{P(OC6Cl3Me-o)(OC6H4Me-o)2}(pyridine)(PMe3)] has been elucidated by X-ray crystallography.