Structure and emission properties of mixed-ligand Cu(I) complexes containing phosphinesulfide ligands

Mixed-ligand Cu(I) complexes containing phosphinesulfide ligands were synthesized, and the structure and emission properties were studied for the Cu(I) complexes. X-ray crystallographic study showed that a chelating phosphinesulfide and diimine are coordinated to Cu(I) center. Coordination geometry around Cu(I) center of each complex is described as a distorted tetrahedron. Some of the complexes show photoluminescence in the solid state.     

Multiple state emission from rhodium(I) and iridium(I) complexes

The effect of temperature (2–100 K) on the emission spectra and lifetimes of [M(2 = phos)₂]ClO₄ (M = Rh(I), Ir(I): 2 = phos is cis-1,2-bis-(diphenylphosphino)ethylene) is interpreted with a two-level spin-orbit-split emitting manifold. For [Ir(2 = phos)₂]ClO₄, Δ? = 143cm^?1, τ(lower) = 999μs, and τ(higher) = 1.54 μs. For the rhodium species, Δ? = 35 cm^?1, τ(lower) = 5920 μs, and τ(higher) = 20.3 μs.     

Cu(I) and Cu(II) helical complexes formed with oligobipyridine ligand

A new asymmetric oligobipyridine ligand, 1- (5’-methyl-2, 2’-bipyridin-5-y1)-2- (6’-methyl-2, 2’-bipyridin-6-yl)ethane (L), in which the bipyridine units are bridged by CH₂CH₂ at 5,6’-position has been synthesized. The ligand L reacts with Cu(I) and Cu(I1) ions giving double-stranded helical complexes [Cu ₂ ¹ L₂](C10₄)₂.Et₂0 (1) and [Cu ₂ ^II L₂,(OH)(H₂0) ] [ClO₄]₃(2), respectively. Complexes 1 and 2 were characterized by X-ray diffraction analyses, ES-MS, ESR and cyclic voltammetry, etc. Differing from the oligobipyridine ligands bridged by CH₂CH₂ at 6,6’-or 5,5’-position, the ligand L not only forms a double-stranded helicate with Cu(1) ion, but also gives a double-stranded helicate with Cu(I1) ion. The results show that the linkage mode of the spacer group to the bipyridine units exerts a great impact on the formation of helix. Project supported by the National Natural Science Foundation of China (Grant NO. 29601003).     

Photosensitized generation of singlet oxygen from rhenium(I) and iridium(III) complexes

Photophysical properties in dilute acetonitrile solution are reported for a number of iridium(III) and rhenium(I) complexes. The nature of the lowest excited state of the complexes under investigation is either metal-to-ligand charge transfer ((3)MLCT) or a ligand centred ((3)LC) state. Rate constants, k(q), for quenching of the lowest excited states by molecular oxygen are in the range 1.5 x 10(8) to 1.4 x 10(10) M(-1) s(-1). Efficiency of singlet oxygen production, f(Delta)(T), following oxygen quenching of the lowest excited states of these complexes, are in the range of 0.27-1.00. The rate constants and the efficiency of singlet oxygen formation are quantitatively reproduced by a model that assumes the competition between a non-charge transfer (nCT) and a CT deactivation channel. The balance between CT and nCT deactivation channels, which is described by the relative contribution p(CT) of CT induced deactivation, is discussed. The kinetic model is found to be successfully applied in the case of quenching of the excited triplet states of coordination compounds by oxygen in acetonitrile, as was proposed for the quenching of pi-pi* triplet states by oxygen.     

Thermal decomposition of Cu(I) phosphine complexes

The thermal decomposition of Cu(I) phosphine complexes of the general types (CuXPPh₃)₄, [CuX(PPh₃)₂] and [CuX(PPh₃)₃] was investigated.The thermal decomposition of (CuXPPh₃)₄, where X denotes Cl^–, Br^–, I^–, NO ₃ ^– and PPh₃=P(C₆H₅)₃, occurs with formation of a phosphine oxide intermediate. For the remaining complexes this intermediate was not proved in the thermal decomposition.

---

Zusammenfassung Die thermische Zersetzung der Cu(I)-Phosphinkomplexe vom allgemeinen Typ (CuXPPh₃)₄ und [CuX(PPh₃)₂], wie auch [CuX(PPh₃)₃] wurde untersucht. Die thermische Zersetzung von (CuXPPh₃)₄, wobei X=Cl^–, Br^–, I^– und NO ₃ ^– bedeutet und PPh₃=P(C₆H₅)₃, verläuft unter Bildung eines Phosphinoxid Zwischenproduktes, bei den übrigen Komplexen konnte dieses im Laufe der thermischen Zersetzung nicht nachgewiesen werden.

---

Résumé On a étudié la décomposition thermique des complexes phosphine-Cu(I) de formule générale (CuXPPh₃)₄, [CuX(PPh₃)₂], [CuX(PPh₃)₃]. La décomposition thermique de (CuXPPh₃)₄, où X désigne Cl^–, Br^–, I^– et NO ₃ ^– , et PPh₃=P(C₆H₅)₃, s'effectue avec formation d'un oxyde de phosphine intermédiaire; avec les autres complexes, cet intermédiaire n'a pas été mis en évidence au cours de la décomposition thermique.

---

(CuXPPb₃)₄ [CuX(PPh₃)₂] [CuX(PPh₃)₃]. (CuXPPh₃)₄, X=Cl^–, Br^–, I^–, NO ₃ ^– , PPh₃=(₆₅)₃ . .

     

Synthesis and characterization of Cu(I) and Cu(II) complexes containing ketiminate ligands

A series of Cu(I) and Cu(II) complexes containing substituted ketiminate ligands was synthesized. Reaction of CuCl₂ with 2 equiv. of Li[OC(Me)CHC(Me)N(Ar)] in toluene generated dark green solid of Cu[OC(Me)CHC(Me)N(Ar)]₂ (1). Similarly, Cu(I) complex, {Cu[OC(Me)CHC(Me)N(Ar)]Li[OC(Me)CHC(Me)N(Ar)]}₂ (2) was synthesized by reacting 2 equiv. of Li[OC(Me)CHC(Me)N(Ar)] with CuCl in toluene at room temperature for 12 h. While the reaction of CuCl with Li[OC(Me)CHC(Me)N(Ar)] in the presence of triphenylphosphine in THF solution at room temperature, a three-coordinated Cu[OC(Me)CHC(Me)N(Ar)](PPh₃) (3) can be isolated in high yield. Replacing the PPh₃ of 3 with N-heterocarbene (NHC) generates Cu[OC(Me)CHC(Me)N(Ar)](NHC) (4) in low yield. Complexes 2, 3, and 4 were characterized by ¹H and ¹³C NMR spectroscopies and all molecules were structurally characterized by X-ray diffractometry. Two coordination modes of ketiminate ligands were found in the molecular structure of 2, one of which is copper-coordinated terminal ketiminates and the other is lithium-copper-coordinated bridging ketiminates.     

Cu(I) complexes with oligo- and polyarylene phosphites

Monovalent copper complexes with oligo- and polyarylene phosphites were obtained. Complexation takes place due to coordination of copper with the phosphorus atom.Translated from Izvestiya Akademii Nauk SSSR, Seriya Khimicheskaya, No. 5, pp. 1198–1201, May, 1991.     

Selenourea complexes of Cu(I), Ag(I), and Au(I) chlorides

Russian Chemical Bulletin -     

Reversed-phase ion-interaction chromatography of Cu(I)-cyanide complexes

It has been established that during the separation of Cu(I)-cyanide complexes, the cyanide:Cu(I) molar ratio, R of the eluted complex remained constant irrespective of the R value injected onto the column, and there was considerable tailing of the unretained cyanide peak and fronting of the Cu(I)-cyanide peak in an eluent containing no cyanide. The addition of small amounts of cyanide (100 μM) to the eluent resulted in the elimination of these effects on peak shape and a significant increase in the retention of the Cu(I)-cyanide species. These results suggested that more than one Cu(I)-cyanide complex may be present in the Cu(I)-cyanide peak in an eluent containing no cyanide. Three different detection systems [Fourier transform Infrared (FTIR) and photodiode array spectrophotometry and a post-column reaction (PCR)], were used to determine changes that occurred to the Cu(I)-cyanide complexes during the separation with eluents containing from 0 to 100 μM cyanide. The FTIR approach was unsuccessful due to a lack of sensitivity. The UV spectrum of the Cu(I) peak in any one eluent remained constant, irrespective of the composition of the injected sample, but there were distinct changes in this spectrum among eluents. Similarly, the R value of the Cu(I) peak determined by PCR remained the same in any one eluent but ranged from about 2.5 to about 3.4 for these eluents. The R value was found to vary within the eluted Cu(I)-cyanide peak, especially in an eluent containing no added cyanide. These results show that more than one Cu(I)-cyanide complex is present in the eluted peak and that in the absence of cyanide in the eluent, the eluted peak consists of a mixture of the di- and tricyano complexes of Cu(I).     

Solid-state (63)Cu and (65)Cu NMR spectroscopy of inorganic and organometallic copper(I) complexes

Solid-state 63Cu and 65Cu NMR experiments have been conducted on a series of inorganic and organometallic copper(I) complexes possessing a variety of spherically asymmetric two-, three-, and four-coordinate Cu coordination environments. Variations in structure and symmetry, and corresponding changes in the electric field gradient (EFG) tensors, yield 63/65Cu quadrupolar coupling constants (CQ) ranging from 22.0 to 71.0 MHz for spherically asymmetric Cu sites. These large quadrupolar interactions result in spectra featuring quadrupolar-dominated central transition patterns with breadths ranging from 760 kHz to 6.7 MHz. Accordingly, Hahn-echo and/or QCPMG pulse sequences were applied in a frequency-stepped manner to rapidly acquire high S/N powder patterns. Significant copper chemical shielding anisotropies (CSAs) are also observed in some cases, ranging from 1000 to 1500 ppm. 31P CP/MAS NMR spectra for complexes featuring 63/65Cu-31P spin pairs exhibit residual dipolar coupling and are simulated to determine both the sign of CQ and the EFG tensor orientations relative to the Cu-P bond axes. X-ray crystallographic data and theoretical (Hartree-Fock and density functional theory) calculations of 63/65Cu EFG and CS tensors are utilized to examine the relationships between NMR interaction tensor parameters, the magnitudes and orientations of the principal components, and molecular structure and symmetry.     

Cu(I)-amido complexes in the Ullmann reaction: reactions of Cu(I)-amido complexes with iodoarenes with and without autocatalysis by CuI

A series of Cu(I)-amido complexes both lacking ancillary ligands and containing 1,10-phenanthroline (phen) as ancillary ligand have been prepared. These complexes react with iodoarenes to form arylamine products, and this reactivity is consistent with the intermediacy of such complexes in catalytic Ullmann amination reactions. The stoichiometric reactions of the Cu(I)-amido complexes with iodoarenes are autocatalytic, with the free CuI generated during the reaction serving as the catalyst. Such autocatalytic behavior was not observed for reactions of iodoarenes with copper(I) amidates, imidates, or phenoxides. The selectivity of these complexes for two sterically distinct aryl halides under various conditions imply that the autocatalytic reaction proceeds by forming highly reactive [CuNPh(2)](n) lacking phen. Reactions with radical probes imply that the reactions of phen-ligated Cu(I)-amido complexes with iodoarenes occur without the intermediacy of aryl radicals. Density functional theory calculations on the oxidative addition of iodoarenes to Cu(I) species are consistent with faster reactions of iodoarenes with CuNPh(2) species lacking phen in DMSO than reactions of iodoarenes with LCuNPh(2) in which L = phen. The free-energy barrier computed for the reaction of PhI with (DMSO)CuNPh(2) was 21.8 kcal/mol, while that for the reaction of PhI with (phen)CuNPh(2) was 33.4 kcal/mol.     

Synthesis and coordination behavior of Cu(I) bis(phosphaethenyl)pyridine complexes

Cu(I) complexes bearing BPEP as a PNP-pincer type phosphaalkene ligand undergo effective bonding interactions with SbF(6)(-) and PF(6)(-) as non-coordinating anions to give [Cu(SbF(6))(BPEP)] and [Cu(2)(BPEP)(2)(μ-PF(6))](+), respectively [BPEP = 2,6-bis(1-phenyl-2-phosphaethenyl)pyridine]. NMR and theoretical studies indicate a reduced anionic charge of the μ-PF(6) ligand, which is induced by the strong π-accepting ability of BPEP.     

Reaction of singlet oxygen with Ir(I) and Rh(I) thiolato complexes: oxidative addition vs. S-oxidation

Singlet oxygen reacts with Ir(I) and Rh(I) thiolato complexes to form the corresponding Ir(III) and Rh(III) peroxo thiolato complexes which do not undergo intramolecular oxidation of the thiolate moiety.     

Kinetics and mechanism of piperidine carbonylation in the presence of Cu(I) and Cu(II) complexes

The kinetics of piperidine carbonylation to bispentamethylenurea in the presence of Cu(I) and Cu(II) complexes has been studied. An adequate mechanism of the process is proposed and the constant of the rate-determining step has been calculated.

---

(I, II) -. .

     

Threshold CID investigation of isomeric Cu(I) azabox complexes

An improved method for deconvoluting energy-resolved collision-induced dissociation cross sections yields ligand binding energies for organometallic complexes with substantially less prior information than before. Application to isomeric 2:1 complexes of azabox ligands with Cu(I) gives consistent results for the binding energies of the ligands to homo- and heterochiral complexes with pseudo-enantiomeric ligands for cases where previous deconvolution methods had failed to give satisfactory results.     

Luminescence tribochromism and bright emission in gold(I) thiouracilate complexes

New dinuclear Au(I) complexes containing bridging thiouracilate and bis(diphenylphosphino)methane ligands have been synthesized and characterized structurally and spectroscopically. The compounds exhibit a unique behavior of solid-state luminescence tribochromism in which photoemission turns on upon gentle grinding of the sample and a sensitivity to pH in fluid solution. The emissive form in the solid state exhibits a bright blue or cyan emission upon irradiating at 375 nm. Structural studies show that the nonemissive form of the complexes has an extended helical ...Au...Au...Au... structure in the solid with weak aurophilic interactions, whereas the blue emissive form has a strong intermolecular aurophilic interaction in the solid that leads to an arrangement of dimers of dinuclear (Au2) complexes. Interconversion between the two forms can be carried out by either recrystallization for solid-state samples or by exposure to vapors of volatile acid or base for fluid solutions of the complexes.     

Phosphorescent Cu(I) complexes of 2-(2'-pyridylbenzimidazolyl)benzene: impact of phosphine ancillary ligands on electronic and photophysical properties of the Cu(I) complexes

Four mononuclear Cu(I) complexes of 2-(2'-pyridyl)benzimidazolylbenzene (pbb) with four different ancillary phosphine ligands PPh(3), bis[2-(diphenylphosphino)phenyl]ether (DPEphos), bis(diphenylphosphino)ethane (dppe), and bis(diphenylphosphinomethyl)diphenylborate (DPPMB) have been synthesized. The crystal structures of [Cu(pbb)(PPh(3))(2)][BF(4)] (1), [Cu(pbb)(dppe)][BF(4)] (2), [Cu(pbb)(DPEphos)][BF(4)] (3), and the neutral complex [Cu(pbb)(DPPMB)] (4) were determined by single-crystal X-ray diffraction analyses. The impact of the phosphine ligands on the structures of the copper(I) complexes was examined, revealing that the most significant impact of the phosphine ligands is on the P-Cu-P bond angle. The electronic and photophysical properties of the new complexes were examined by using UV-vis, fluorescence, and phosphorescence spectroscopies and electrochemical analysis. All four complexes display a weak MLCT absorption band that varies considerably with the phosphine ligand. At ambient temperature, no emission was observed for any of the complexes in solution. However, when doped into PMMA polymer (20 wt %), at ambient temperature, all four complexes emit light with a color ranging from green to red-orange, depending on the phosphine ligand. The emission of the new copper complexes has an exceptionally long decay lifetime (>200 micros). Ab initio MO calculations established that the lowest electronic transition in the copper(I) complexes is MLCT in nature. The electronic and photophysical properties of the new mononuclear Cu(I) complexes were compared with those of the corresponding polynuclear Cu(I) complexes based on the 2-(2'-dipyridyl)benzimidazolyl derivative ligands and the previously extensively studied phenanthroline-based Cu(I) complexes.     

Supramolecular double helical Cu(I) complexes for asymmetric cyclopropanation

Chiral double-stranded helicates, formed between Cu(I) ion and C(2)-symmetric oligopyridines, were used for catalytic asymmetric cyclopropanation of alkenes; low catalyst loadings (0.2 mol%), high TONs (up to 404) and short reaction times (30-60 min) were achieved with [Cu(2)L(2)]OTf(2)(L = chiral C(2)-symmetric terpyridine).     

Simple Cu(I) complexes with unprecedented excited-state lifetimes.

This report describes new, readily accessible copper(I) complexes that can exhibit unusually long-lived, high quantum yield emissions in fluid solution. The complexes are of the form [Cu(NN)(POP)]+ where NN denotes 1,10-phenanthroline (phen), 2,9-dimethyl-1,10-phenanthroline (dmp) or 2,9-di-n-butyl-1,10-phenanthroline (dbp) and POP denotes bis[2-(diphenylphosphino)phenyl] ether. Modes of characterization include X-ray crystallography and cyclic voltammetry. The complexes each have a pseudotetrahedral coordination geometry and a Cu(II)/Cu(I) potential upward of +1.2 V vs Ag/AgCl. In room-temperature dichloromethane solution, charge-transfer excited states of the dmp and dbp derivatives exhibit respective emission quantum yields of 0.15 and 0.16 and corresponding excited-state lifetimes of 14.3 and 16.1 mus, respectively. Despite the fact that coordinating solvents usually quench charge-transfer emission from copper systems, the photoexcited dmp (dbp) complex retains a lifetime of 2.4 mus (5.4 mus) in methanol.     

Interaction of Cu(I) carbonyl with Pd(II) and Cu(II) complexes in aqueous and nonaqueous media

CO hydrogenation over Ni-rutile and Ni-anatase catalysts has been studied at 470–520 K. Activity of the rutile catalyst is by an order of magnitude higher and it produces C₁–C₁₅-hydrocarbons; the anatase sample yields only C₁–C₃-paraffins. At 310–330 K the Ni-anatase catalyst loses nickel, while the nickel content in the Ni-rutile sample remains practically unchanged.

---

CO - 470–520 , ; C₁–C₁₅; — C₁–C₃. 310–330 - , .