Reactivity Of Complexes Research Articles

Reactions of Platinum Terminal Polyynyl Complexes trans-(C6F5)(p-tol3P)2Pt(C≡C)nH (n = 2-4) and n-BuLi, Generation of Functional Equivalents of Pt(C≡C)nLi Species, and Derivatization with Organic and Inorganic Electrophiles.

Reactions of the title complexes and n-BuLi (1.5 equiv, -45 °C) afford functional equivalents of the deprotonated species trans-(C6F5)(p-tol3P)2Pt(C≡C)nLi (n = 2-4), as assayed by subsequent additions of MeI or Me3SiCl to give trans-(C6F5)(p-tol3P)2Pt(C≡C)nMe (66-52%) or trans-(C6F5)(p-tol3P)2Pt(C≡C)nSiMe3 (63-49%). However, 31P NMR data suggest more complicated mechanistic scenarios, and small amounts of the hydride complex trans-(C6F5)(p-tol3P)2PtH (independently synthesized from the chloride complex, AgClO4, and NaBH4) are detected in most cases. Analogous sequences involving trans-(C6F5)(p-tol3P)2Pt(C≡C)2H and benzyl bromide, D2O, or W(CO)6/Me3O+ BF4- similarly afford products with Pt(C≡C)2Bn, Pt(C≡C)2D, or Pt(C≡C)2C(OCH3)=W(CO)5 linkages. The crystal structures of the tungsten and corresponding SiMe3 adduct, the three Pt(C≡C)nMe species, and hydride complex are determined.

Nitrosyl derivatives of the halide-bridged complexes [M2Cp2(μ-X)(μ-PtBu2)(CO)2] (M = Mo, W; X = Cl, I).

The title compounds were prepared as described previously (M = Mo, X = Cl) or by the reaction of the known unsaturated complex [W2Cp2(μ-PtBu2)(CO)4]BF4 with NaI in refluxing 1,2-dichloroethane solution. Reaction of these halide-bridged complexes with NO (1 atm) at low temperature yielded the corresponding dinitrosyl derivatives syn,trans-[M2Cp2X(μ-PtBu2)(CO)(NO)2], with a syn arrangement of Cp ligands relative to the M2P plane, and a transoid arrangement of the halide ligand X relative to the P atom, according to an X-ray study on the ditungsten complex (W−W = 3.113(1) Å). Further decarbonylation of these products at high temperature yielded in both cases the halide-bridged complexes trans-[M2Cp2(μ-X)(μ-PtBu2)(NO)2] as major products, but the minor products were different. For the molybdenum complex, an isomer of the final product, cis-[Mo2Cp2(μ-Cl)(μ-PtBu2)(NO)2], was formed. In contrast, the minor tungsten product, anti,cis-[W2Cp2I(μ-PtBu2)(CO)(NO)2], was an isomer of the parent complex. In addition, trace amounts of the imide cyclopentadienylidene complex [W2Cp(μ-κ:η5-C5H4)I(μ-PtBu2)(NH)(NO)] was also obtained (W−W = 2.9376(2) Å). Density functional theory calculations were used to examine possible routes to the above dinitrosyl complexes, that seem to involve at least three reaction pathways: direct decarbonylation, rearrangement of the MCpX(NO) fragment prior to decarbonylation, and rearrangement of the MCp(CO)(NO) fragment prior to decarbonylation.

Mechanistic Aspects of Redox Reactions of Transition Metal Complexes in Aqueous Media

Mechanistic Aspects of Redox Reactions of Transition Metal Complexes in Aqueous Media

Dinitrogen Cleavage and Multicoupling with Isocyanides in a Dititanium Dihydride Framework.

Dinitrogen (N2) activation and functionalization through N-N bond cleavage and N-C bond formation are of great interest and importance but remain highly challenging. We report here for the first time N2 cleavage and selective multicoupling with isocyanides in a dititanium dihydride framework. The reaction of a dinitrogen dititanium dihydride complex [{(acriPNP)Ti}2(μ-η1:η2-N2)(μ-H)2] (1) with an excess (four or more equivalents) of p-methoxyphenyl isocyanide at room temperature gave a novel amidoamidinatoguanidinate complex [(acriPNP)Ti{NC(═NR)NC(═NR)CH2NR}Ti(acriPNP)(CNR)] (2, acriPNP = 4,5-bis(diisopropylphosphino)-2,7,9,9-tetramethyl-9H-acridin-10-ide; R = p-MeOC6H4) through N2 splitting and coupling with three isocyanide molecules. When 1 equiv of p-methoxyphenyl isocyanide was used to react with 1 at -30 °C, the hydrogenation of the isocyanide unit by the two hydride ligands in 1 took place, affording an amidomethylene-bridged dititanium dinitrogen complex [{(acriPNP)Ti}2(μ-η1:η2-N2){μ-η1:η2-CH2N(p-MeOC6H4)}] (3), which upon reaction with another equivalent of p-methoxyphenyl isocyanide at room temperature gave an amidomethylene/nitrido/carbodiimido complex [(acriPNP)Ti(N═C═NR)(μ-N)(μ-η1:η2-CH2NR)Ti(acriPNP)] (4) through N2 cleavage and N═C bond formation. Further reaction of 4 with 1 equiv of p-methoxyphenyl isocyanide led to an unprecedented four-component (carbodiimido, nitrido, isocyanide, and amidomethylene) coupling, yielding an amidoamidinatoguanidinate complex [{(acriPNP)Ti}2{NC(═NR)NC(═NR)CH2NR}] (5), which on reaction with another equivalent of p-methoxyphenyl isocyanide afforded the isocyanide-coordinated analogue 2. The reaction of 1 with 2-naphthyl isocyanide also took place in a similar multicoupling fashion. Moreover, the cross-coupling reactions of the p-methoxyphenyl isocyanide-derived amidomethylene/nitrido/carbodiimido complex 4 with 2-naphthyl isocyanide, cyclohexyl isocyanide, and tert-butyl isocyanide were also achieved, which afforded the corresponding amidoamidinatoguanidinate products consisting of two different isocyanides. Density functional theory (DFT) calculations further elucidated the mechanistic details.

Development of a new sterilization method for microalgae media using calcium hypochlorite as the sterilant.

Calcium hypochlorite (Ca(ClO)2), which can be stably stored in powder form for a long period, is widely used as a disinfectant in various fields. A new sterilization process was developed in the present study, where a microalgal medium was sterilized using 0.02% Ca(ClO)2, followed by complete neutralization of the Ca(ClO)2 within 8h through catalytic reaction of an MnCl2-Na2EDTA complex and a synergistic effect of glucose. When comparing the growth of Chlorella vulgaris in the autoclaved medium, a 2.65 times greater maximum cell growth was observed in cells grown in the medium prepared by treatment of Ca(ClO)2. This result indicates that denaturation of the medium by heat can hinder the growth of some microorganisms. In the case of cultivation of Euglena gracilis, successful culture growth was achieved without growth inhibition or contamination on a medium prepared in the same manner.

BF3-Promoted Ring Expansion of Iminylphosphiranes and Acylphosphiranes for Divergent Access to 1,2-Azaphospholidines and 1,2-Dihydrophosphetes.

Ring expansion of strained small rings provides an efficient method for the synthesis of various high-value carbocycles and heterocycles. Here we report BF3·Et2O as both an activating reagent and fluorine source, enabling ring expansion of phosphirane and P-F bond formation. Treatment of 1-iminylphosphirane complexes with BF3·Et2O resulted in 1,2-azaphospholidines, while the reaction of 1-acylphosphirane complexes with BF3·Et2O afforded 1,2-dihydrophosphetes. The reaction path was tuned by the nucleophilicity of the N and O atoms toward the intermediate phosphenium cation.

Alkane Elimination Preparation of Heterobimetallic MoAl Tetranuclear and Binuclear Complexes Promoting THF Ring Opening

We report a straightforward alkane elimination strategy to prepare well-defined heterobimetallic Al/Mo species. Notably, the reaction of the monohydride complex of molybdenum, Cp*MoH(CO)3, with triisobutyl aluminum affords a new heterobimetallic [MoAl]2 tetranuclear compound, [Cp*Mo(CO)(µ-CO)2Al(iBu)2]2, (1), featuring a 12-membered C4O4Mo2Al2 ring in which isocarbonyls bridge the Mo and Al centers. The addition of pyridine to this complex successfully results in the dissociation of the dimer into a new discrete binuclear complex, [Cp*Mo(CO)2(µ-CO)Al(Py)(iBu)2], (2). Switching the nature of the Lewis base from pyridine to tetrahydrofuran does not lead to the THF analogue of adduct 2, but rather to a complex reaction where one of the identified products corresponds to a tetranuclear species, [Cp*Mo(CO)3(μ-CH2CH2CH2CH2O)Al(iBu)2]2, (3), featuring two bridging alkoxybutyl fragments originating from the C-O ring opening of THF. Compound 3 adds to the unusual occurrences of THF ring opening by heterobimetallic complexes, which is evocative of masked metal-only frustrated Lewis pair behavior and highlights the high reactivity of these Al/Mo assemblies.

Generation and Reactivity of Polychalcogenide Chains in Binuclear Cobalt(II) Complexes.

A series of six binuclear Co(II)-thiolate complexes, [Co2(BPMP)(S-C6H4-o-X)2]1+ (X = OMe, 2; NH2, 3), [Co2(BPMP)(μ-S-C6H4-o-O)]1+ (4), and [Co2(BPMP)(μ-Y)]1+ (Y = bdt, 5; tdt, 6; mnt, 7), has been synthesized from [Co2(BPMP)(MeOH)2(Cl)2]1+ (1a) and [Co2(BPMP)(Cl)2]1+ (1b), where BPMP1- is the anion of 2,6-bis[[bis(2-pyridylmethyl)amino]methyl]-4-methylphenol. While 2 and 3 could allow the two-electron redox reaction of the two coordinated thiolates with elemental sulfur (S8) to generate [Co2(BPMP)(μ-S5)]1+ (8), the complexes, 4-7, could not undergo a similar reaction. An analogous redox reaction of 2 with elemental selenium ([Se]) produced [{Co2(BPMP)(μ-Se4)}{Co2(BPMP)(μ-Se3)}]2+ (9a) and [Co2(BPMP)(μ-Se4)]1+ (9b). Further reaction of these polychalcogenido complexes, 8 and 9a/9b, with PPh3 allowed the isolation of [Co2(BPMP)(μ-S)]1+ (10) and [Co2(BPMP)(μ-Se2)]1+ (11), which, in turn, could be converted back to 8 and 9a upon treatment with S8 and [Se], respectively. Interestingly, while the redox reaction of the polyselenide chains in 9a and 11 with S8 produced 8 and [Se], the treatment of 8 with [Se] gave back only the starting material (8), thus demonstrating the different redox behavior of sulfur and selenium. Furthermore, the reaction of 8 and 9a/9b with activated alkynes and cyanide (CN-) allowed the isolation of the complexes, [Co2(BPMP)(μ-E2C2(CO2R)2)]1+ (E = S: 12a, R = Me; 12b, R = Et; E = Se: 13a, R = Me; 13b, R = Et) and [Co2(BPMP)(μ-SH)(NCS)2] (14), respectively. The present work, thus, provides an interesting synthetic strategy, interconversions, and detailed comparative reactivity of binuclear Co(II)-polychalcogenido complexes.

Synthesis, Structure, and Reactivity of Molybdenum- and Tungsten-Indane Complexes with Tris(pyrazolyl)borate Ligand.

The reaction of molybdenum complexes with a tris(pyrazolyl)borate ligand (Et4N[TpMo(CO)3] and Et4N[Tp*Mo(CO)3] (Tp = hydridotris(pyrazolyl)borate, Tp* = hydridotris(3,5-dimethylpyrazolyl)borate)) and InBr3 at a 1:1 molar ratio afforded molybdenum-indane complexes (Et4N[TpMo(CO)3(InBr3)] 1 and Et4N[Tp*Mo(CO)3(InBr3)] 2). In addition, tungsten-indane complexes, Et4N[TpW(CO)3(InBr3)] 3 and Et4N[Tp*W(CO)3(InBr3)] 4, were obtained by the reaction of corresponding tungsten complexes. Complex 4 reacted with H2O to form the hydrido complex Tp*W(CO)3H, in which the W-In bond was cleaved. On the other hand, 4 reacted with three equiv. of AgNO3 to form Et4N[Tp*W(CO)3{In(ONO2)}] 5, in which three substituents on the In were exchanged while retaining the W-In dative bond. Complexes 1-5 were fully characterized using NMR measurements and elemental analyses, and the structures of 1-5 and Et4N[Tp*W(CO)3] were determined via X-ray crystallography. These are the first examples of mononuclear molybdenum- and tungsten-indane complexes with Mo-In and W-In dative bonds.

Radical Cations of Bilayer Nanographenes.

Chemical redox reactions of bilayer nanographene complexes, (C96H24Ar6)2 (Ar = 2,6-dimethylphenyl) (12) and (C42H12R6)2 (R = tBu) (22), were investigated. Upon two-electron oxidation reactions, 12 and 22 were transformed to radical cations 122•+ and 222•+, respectively. SQUID and EPR measurements on 122•+ and 222•+ indicate that they possess an open-shell singlet ground state with antiferromagnetic interactions between two layers. The shortest separation distance between bilayers in 222•+ (3.30 Å) is shorter than that in 22 (3.44 Å) and 22•+ (3.40 Å), illustrating stronger interaction upon loss of electrons.

Reaction Stability Test of Hexavalent Chromium Complex with 1,5-Diphenylcarbazide in Analysis using UV Visible Spectrophotometer

A reaction stability test of hexavalent chromium complex with 1,5-diphenyl carbazide in analysis using a UV Visible Spectrophotometer has been done in this study. This study aims to find out the colored complex stability for the reaction of chromium hexavalent and diphenyl carbazide in the analysis of hexavalent chromium using a UV Vis spectrophotometer in terms of time. The sample was measured in 540 nm of wavelength with 10, 30, 60, 90, 120, and 180-minute time intervals. Each interval was carried out with two times replications. There were no significant differences in the colored complex until the 180-minute time interval, and the measurement of Cr(VI) concentration showed similar results. This analysis exhibits a level of precision and accuracy, evident from the RPD values below 10 % and the recovery values falling within the range of 90 – 110 %. It means that the reaction of hexavalent chromium complex with 1,5-diphenyl carbazide in analysis using a UV Visible Spectrophotometer is stable.

Reactions of neutral chromium silylyne complex with alkynes and butadiene: access to homoaromatic compounds and silacyclopentenyl complexes

Abstract Reactions of a chromium complex, featuring a Cr≡Si triple bond, with alkynes and butadiene were investigated. The former reaction yielded 4-membered metallasilacycles with a homoaromatic character through [2+2] cycloaddition, while the latter reaction afforded silacyclopentenyl complexes through [2+4] cycloaddition.

Two birds with one stone: An innovative fluorescent cellulose polyacrylamide-hydrogel modified by born/nitrogen-doped carbon dots with sensitive visual sensing and superior extraction capacity toward Ag+

Since the last decade, water pollution by silver ions (Ag+) has been a serious potential threat to environmental protection and an enormous research effort has been put into the detection and removal of environmental Ag+. Here, we report a novel fluorescent cellulose polyacrylamide-hydrogel (FCPH) modified by boron/nitrogen doped carbon dots (BN-CDs) for sensitive visual detection and efficient extraction of Ag+. In addition, the introduction of BN-CDs in the cross-linking process promotes the formation of 3D network structures with more ionic adsorption sites in FCPH. On the one hand, the FCPH exhibits an excellent sensing performance in the range of 0–300 μM with a limit detection of 51 nM. On the other hand, the adsorption experiments confirm that the FCPH exhibits an excellent Ag+ extraction performance of over 251.4 mg‧g−1, and the adsorption results accord well with the pseudo-second-order model and the Langmuir model. Detailed mechanism characterizations reveal that the excellent adsorption capacity of FCPH is caused by the redox reaction and formation of metal complexes between the surface functional groups of BN-CDs and Ag+ in FCPH. Hence, this work fabricates a bifunctional hydrogel and provides a convenient “two birds with one stone” strategy for the visual sensing and extraction of Ag+.

Reactions of a geminal Sc/P Lewis pair with pyridotetrazole and beyond.

Frustrated Lewis pair (FLP) chemistry has undergone remarkable growth, among which rare-earth metal-based Lewis pairs have exhibited unique reactivity in recent years. Herein, treatment of the intramolecular Sc/P Lewis pair, i.e., (ArO)2ScN(tBu)PPh2 (1, Ar = 2,6-tBu2-C6H3), with pyridotetrazole resulted in the formation of an FLP nitrene adduct with N2 elimination, offering additional insights into the mechanism of transition-metal-catalyzed denitrogenative annulation of pyridotetrazole. Reactions of complex 1 with 1,3,5-triazine and benzo[c]cinnoline generated FLP-type products via Sc/P 1,2-addition to the CN bond and the NN bond, respectively. Furthermore, treatments of 1 with phenylacetylene, diazo, and azide compounds were also investigated, leading to the formation of a variety of metallacyclic complexes displaying typical FLP behaviors.

Precise analyses of photoelectrochemical reactions on particulate Zn0.25Cd0.75Se photoanodes in nonaqueous electrolytes using Ru bipyridyl complexes as a probe.

Recombination of photoexcited carriers at interface states is generally believed to strongly govern the photoelectrochemical (PEC) performance of semiconductors in electrolytes. Sacrificial reagents (e.g., methanol or Na2SO3) are often used to assess the ideal PEC performance of photoanodes in cases of minimised interfacial recombination kinetics as well as accelerated surface reaction kinetics. However, varying the sacrificial reagents in the electrolyte means simultaneously changing the equilibrium potential and the number of electrons required to perform the sacrificial reaction, and thus the thermodynamic and kinetic aspects of the PEC reactions cannot be distinguished. In the present study, we propose an alternative methodology to experimentally evaluate the energy levels of interfacial recombination centres that can reduce PEC performance. We prepare nonaqueous electrolytes containing three different Ru complexes with different bipyridyl ligands; redox reactions of Ru complexes represent one-electron processes with similar charge transfer rates and diffusion coefficients. Therefore, the Ru complexes can serve as a probe to isolate and evaluate only the thermodynamic aspects of PEC reactions. Recombination centres at the interface between a nonaqueous electrolyte and a Zn0.25Cd0.75Se particulate photoanode are elucidated using this method as a model case. The energy level at which photocorrosion proceeds is also determined.

Synthesis and structures of cobalt-expanded zirconium- and cerium-oxo clusters as precursors for mixed-metal oxide thin films.

Transforming current complementary metal-oxide-semiconductor (CMOS) technology to fabricate memory chips and microprocessors into environmentally friendlier electronics requires the development of new approaches to resource- and energy-efficient electron transport and switching materials. Metal and multi-metal oxide layers play a key role in high-end technical applications. However, these layers are commonly produced through high-energy and high-temperature procedures. Herein, we demonstrate our first attempts to obtain stimuli-responsive mixed-metal oxide thin films from solution-processed molecular precursors under milder conditions. The molecular compounds of interest were prepared by one-pot reactions of a CoII carboxylate complex, triethylamine (Et3N), N-butyldiethanolamine (H2bda), and a hexanuclear complex [Ce6O4(OH)4(piv)12] (Hpiv = pivalic acid) or [Zr6O4(OH)4(ib)12(H2O)]·3Hib (Hib = isobutyric acid) in acetonitrile solution. The resulting charge-neutral, heterometallic coordination compounds display a ligand-supported pentanuclear {CeIV3CoIII2} core (in 1) and a dodecanuclear {ZrIV6CoII6} core (in 2), exhibiting thermal stability up to ca. 100 °C in air. Compound 2 was deposited and analyzed on Au(111) and SiO2/Si(100) surfaces to explore its potential as a single-molecule precursor for the preparation of atomically precise, complex mixed-metal oxide thin films. The adsorption characteristics of it demonstrate the ability to form stable agglomerates on the investigated surfaces.

Supramolecular compounds assembled from the heteroleptic tetrahedral complex [{CpMo(CO)2}2(μ,η2-AsSb)] and metal salts.

The reaction of the tetrahedral complex [{CpMo(CO)2}2(μ,η2-AsSb)] with CuI and AgI salts is presented which gives unprecedented neutral and cationic supramolecular aggregates featuring mixed As/Sb-donor molecules as ligands/linkers between metal ions.

Exploring the carbonic anhydrase-mimetic [(PMDTA)2ZnII2(OH-)2]2+ for nitric oxide monooxygenation.

In biology, nitrite (NO2-) serves as a storage pool of nitric oxide (NO); however, the formation of NO2- from NO is still under investigation. Here, we report the NO monooxygenation (NOM) reaction of a ZnII-hydroxide complex (1), producing a ZnII-nitrito complex {2, (ZnII-NO2-)} + H2.

Reactions of cyclonickelated complexes with hydroxylamines and TEMPO˙: isolation of new TEMPOH adducts of Ni(II) and their reactivities with nucleophiles and oxidants.

This contribution describes a study on the reactivities of the complexes [{κP,κC-(i-Pr)2PO-Ar}Ni(μ-Br)]2, 1a-d (Ar: C6H4, a; 3-Cl-C6H3, b; 3-OMe-C6H3, c; 4-OMe-napthalenyl, d), with hydroxylamines in the presence of TEMPO˙ (TEMPO˙ = (2,2,6,6-tetramethylpiperidinyl-1-yl)oxyl). The results of this study showed that treating 1a-d with a mixture of Et2NOH and TEMPO˙ did not afford the desired oxidation-induced functionalization of the Ni-aryl moiety in 1a-d, giving instead the corresponding κO-TEMPOH adducts [{κP,κC-(i-Pr)2PO-Ar}Ni(Br)(κO-TEMPOH)], 3a-d (TEMPOH = N-hydroxy-2,2,6,6-tetramethylpiperidine). The TEMPOH moiety in these zwitterionic compounds 3 can be displaced by a large excess of acetonitrile (MeCN), 10 equiv. of morpholine, or 1-2 equivalents of imidazole. Although these reactions have given the authenticated products [{κP,κC-(i-Pr)2PO-C6H4}Ni(Br)(NCMe)], 4a, [{κP,κC-(i-Pr)2PO-C6H4}Ni(Br)(morpholine)], 5a, and [{κP,κC-(i-Pr)2PO-C6H4}Ni(imidazole)2]Br, 6a, a few other products were also detected by NMR, indicating that the observed reactivities are far more complex than simple substitution of the TEMPOH moiety. Similarly, treating 3a with AgOC(O)CF3 results in the isolation of [{κP,κC-(i-Pr)2PO-C6H4}Ni{OC(O)CF3}(κO-TEMPOH)], 7a, arising from the substitution of the bromo ligand, whereas spectroscopic evidence suggests further reactivity, possibly including displacement of TEMPOH and oxidative decomposition.

Oxidation-induced coupling reactions of bi(metallacycloprop-1-ene) complexes.

The feasibility of coupling of two carbene ligands of biscarbene complexes LnM(CR2)2 to form alkene complexes LnM(η2-R2CCR2) was predicted theoretically as early as 1982. However, until now, there appear still no reports on carbene coupling reactions of well-defined biscarbene complexes. This work reports oxidation-induced coupling reactions of bi(metallacycloprop-1-ene) complexes to give η4-butadiene complexes, a unique example of coupling of two carbene ligands of biscarbene complexes.