Acetate Complexes Research Articles

A series of ruthenium(II) organometallic complexes incorporating pyridine-2-carboxylato ligand: Detailed spectroscopic and computional studies

The reaction of Ru(κ2C,O-RL)(PPh3)2(CO)Cl, 1 with excess sodium salt of pyridine-2-carboxylic acid (Napic) furnishes the complexes of the type Ru(κ1C-RL)(PPh3)2(CO) (pic), 2(R) with excellent yield (κ2C,O-RL is C6H2O-2-CHNHC6H4R(p)-3-Me-5, κ1C-RL is C6H2OH-2-CHNC6H4R(p)-3-Me-5 and R is Me, OMe, Cl). The chelation of pic is attended with the cleavage of Ru–O and Ru–Cl bonds and iminium–phenolato→imine–phenol prototropic shift. The 1 ​→ ​2 conversion is irreversible and the type 2 species are thermodynamically more stable than the acetate, nitrite and nitrate complexes of 1. The spectral (UV–vis, IR, 1H NMR) and electrochemical data of the complexes are reported. In dichloromethane solution the complexes display one quasi–reversible RuIII/RuII cyclic voltammetric response with E1/2 in the range 0.72–0.80 ​V vs. Ag/AgCl. The crystal and molecular structure of Ru(κ1C-MeOL)(PPh3)2(CO)(pic)∙CH3CN is reported which revealed distorted octahedral RuC2P2NO coordination sphere. The pairs (P, P), (C, O) and (C, N) define the three trans directions. The electronic structures of the complexes are also scrutinized by density functional theory (DFT) and time–dependent density functional theory (TD–DFT) calculations.

Synthesis and characterization of a novel nickel pillared–clay catalyst: In-situ carbon nanotube–clay hybrid nanofiller from Ni-PILC

This work presents a novel synthesis of a nickel complex to fabricate Ni-pillared clay (Ni-PILC) as the supporting catalyst for the synthesis of carbon nanotubes (CNTs). To identify the synthesized complex structure, Fourier transform infrared spectroscopy (FTIR), X-ray diffraction (XRD), thermogravimetric analysis (TGA), elemental analysis, and X-ray photoelectron spectroscopy (XPS) were applied to propose the hexanuclear acetato-ammonia nickel(II) acetate complex, with the chemical formula of [Ni6(OOCCH3)11(NH3)·7H2O]+(OOCCH3)−. Various concentrations of the nickel complex (0.5, 1, 2, 3, 4, 5, 6, 7, and 8 CECs) were used to instigate the ion exchange reaction with the montmorillonite (Mt) surface. Chemical vapor deposition was used to synthesize CNTs. XRD, TGA, Raman, SEM, and TEM characterizations were performed on the CNTs to investigate the influence of the catalyst concentration on the properties of CNTs. Depending on the catalyst concentration, the mass loss of CNTs varied from 28% at 0.5 CEC of the Ni catalyst to ~70% at 8 CEC of the Ni complex. XRD indicated that Na+Mt. layers were intercalated with nickel species during the ion-exchange processes, and then delaminated due to the growth of CNTs. The introduction of higher concentrations of the nickel salt into Mt. improved the quality and the synthesis yield.

Toward N-heterocyclic carbene stabilized zinc sulfides

A series of N-heterocyclic carbene (NHC) supported group 12 acetate complexes were prepared and their use as building blocks toward soluble group 12 sulfide precursors was explored. The highly moisture-sensitive NHC-ligated zinc dithiolato complex [(IPr)Zn(SSiMe3)2] was also synthesized [IPr = 1,3-bis(2,6-diisopropylphenyl)imidazol-2-ylidene], and its partial hydrolysis gave the dianionic zinc sulfide cluster [Zn3(μ3-S)(μ2-SSiMe3)3(SSiMe3)3]2−, which contained a rare example of a Zn3S structural motif. This preliminary observation indicates that the future growth of related metallosulfide clusters from [(IPr)Zn(SSiMe3)2] should be possible.

Single crystal growth, structural characterization and magnetic properties study of an antiferromagnetic trinuclear iron(III) acetate complex with uncoordinated hexamine

Structural characterization of novel Fe(III) basic acetate with 1,3,5,7-tetraazaadamantane (hexamine – HEX), [Fe3(μ3-O)(OAc)6(H2O)3)](NO3)(HEX)2(H2O)5] (1), revealed a molecular structure typical for Fe(III) basic carboxylates, with a triangular array formed by three iron atoms being equilateral and with an uncoordinated hexamine molecule and nitrate anion present in the crystal structure. Despite the hexamine molecule being uncoordinated, it plays a crucial role in the formation of a supramolecular network. The magnetic properties of the compound were characterized by magnetic susceptibility, Mössbauer and EPR spectroscopy. These studies indicate the presence of high-spin iron ions in +3 oxidation state with non-Curie-like behaviour. A small room temperature value of the effective magnetic moment and a decrease of the product χT with decreasing temperature both speak in favour of antiferromagnetic interactions between the three individual Fe(III) ions of complex 1 with a total ground state spin of St = 1/2 per trinuclear cluster. EPR spectroscopy confirmed the formation of a St = 1/2 ground state, but also suggested the presence of weak intermolecular exchange interactions between two (or more) clusters of neighbouring molecules. The temperature-dependent Mössbauer spectra show a slowing-down of the fast spin-lattice relaxation rates of the paramagnetic Fe(III) ion below about 60 K, however, yet no static spin regime is reached down to 3.6 K.

Synthesis of (NH4)2Ta2O3F6 mesocrystals via a hydrothermal route and their conversion to TaO2F and Ta2O5 mesocrystals for photocatalytic dyes degradation

(NH4)2Ta2O3F6 mesocrystals were constructed by oriented self-assembly ultra-fine subunits (nanosheets or nanobelts) via a one-step hydrothermal process. The influence of hydrothermal temperatures and reaction time was also investigated, which (NH4)2Ta2O3F6 mesocrystals were preferred to form under a higher hydrothermal temperature (>180 °C) and a longer reaction time (>6 h), otherwise the occurrence of C7H8N4O2. The addition of acetic acid hindered the hydrolysis process of Ta ions by forming intermediate tantalum acetate complex ions ([(CH3COO)xTaF6-x]-) instead of [TaOF3·2F]2−, and their subsequent hydrolysis-condensation process controlled the morphology evolution of (NH4)2Ta2O3F6 mesocrystals. More importantly, the mesocrystal precursor transformation strategy was employed to synthesize tantalum-based oxides nanomaterials, by calcining the (NH4)2Ta2O3F6 mesocrystals ranging from 400-1200 °C. Mesocrystalline TaO2F nanosheets were formed after heat-treatment at 400 and 500 °C, Ta2O5 nanorods occurred as the annealing temperature is higher than 800 °C. The as-synthesized (NH4)2Ta2O3F6, TaO2F and Ta2O5 mesocrystals were evaluated as photocatalysts on the methylene blue (MB) degradation efficiency, which exhibited enhanced photocatalytic performance except for sample (NH4)2Ta2O3F6-180, in comparison with commercial nanosized Ta2O5 powders. Kinetics analysis indicated that photocatalytic degradation of MB to these samples followed the pseudo-first order model. Particularly, the highest photocatalytic activity was obtained by sample (NH4)2Ta2O3F6-160 with a rate constant of 0.018 min−1, which was nearly 9 times that of commercial Ta2O5 powders.

Green Procedure for Aerobic Oxidation of Benzylic Alcohols with Palladium Supported on Iota-Carrageenan in Ethanol.

The search for selective heterogeneous catalysts for the aerobic oxidation of alcohols to ketones and aldehydes has drawn much attention in the last decade. To that end, different palladium-based catalysts have been proposed that use various organic and inorganic supports. In addition, supports that originate from a biological and renewable source that is also nontoxic and biodegradable were found to be superior. We heterogenized palladium chloride or acetate complexes with triphenylphosphine trisulfonate on iota-carrageenan xerogel by simple mixing of the complex and the polysaccharide in water. The resulting polysaccharide-catalyst mixture then underwent deep freeze and lyophilization, after which the catalyst was characterized by TEM, XPS and SEM-EDS and tested in aerobic oxidation. The new heterogeneous catalysts were successfully used for the first time in the aerobic oxidation of benzylic alcohols. Moreover, they were easily removed from the reaction mixture and recycled, yielding an increase in activity with each subsequent reuse. As determined by TEM and XPS, the reduction in palladium and the formation of nanoparticles during the reaction in ethanol yielded more active species and, therefore, higher conversion rates. A SEM-EDS analysis indicated that the palladium was thoroughly dispersed in the xerogel catalysts. Moreover, the xerogel catalyst was observed to undergo a structural change during the reaction. To conclude, the new heterogeneous catalyst was prepared by a simple and straightforward method that used a non-toxic, renewable and biodegradable support to yield an active, selective and recyclable heterogeneous system.

X-ray Crystallographic Snapshots of Substrate Binding in the Active Site of Histone Deacetylase 10.

Histone deacetylase 10 (HDAC10) is a zinc-dependent polyamine deacetylase enriched in the cytosol of eukaryotic cells. The active site of HDAC10 contains catalytic residues conserved in other HDAC isozymes that function as lysine deacetylases: Y307 assists the zinc ion in polarizing the substrate carbonyl for nucleophilic attack, and the H136-H137 dyad serves general base-general acid functions. As an inducer of autophagy, HDAC10 is an attractive target for the design of selective inhibitors that may be useful in cancer chemotherapy. Because detailed structural information regarding the catalytic mechanism of HDAC10 may inform new approaches to inhibitor design, we now report X-ray crystal structures of HDAC10 in which reaction intermediates with substrates N8-acetylspermidine and N-acetylputrescine are trapped in the active site. The Y307F substitution prevents activation of the substrate carbonyl for nucleophilic attack by the zinc-bound water molecule, thereby enabling crystallographic isolation of intact enzyme-substrate complexes. The H137A substitution removes the catalytically obligatory general acid, thereby enabling crystallographic isolation of oxyanionic tetrahedral intermediates. Finally, the acetate complex with the wild-type enzyme represents a product complex after dissociation of the polyamine coproduct. Taken together, these structures provide snapshots of the reaction coordinate of acetylpolyamine hydrolysis and are consistent with a mechanism in which tandem histidine residues H136 and H137 serve as general base and general acid catalysts, respectively. The function of the histidine dyad in the HDAC10 mechanism appears to be similar to that in HDAC6, but not HDAC8 in which both functions are served by the second histidine of the tandem pair.

Advancing understanding of actinide(iii) (Ac, Am, Cm) aqueous complexation chemistry.

The positive impact of having access to well-defined starting materials for applied actinide technologies – and for technologies based on other elements – cannot be overstated. Of numerous relevant 5f-element starting materials, those in complexing aqueous media find widespread use. Consider acetic acid/acetate buffered solutions as an example. These solutions provide entry into diverse technologies, from small-scale production of actinide metal to preparing radiolabeled chelates for medical applications. However, like so many aqueous solutions that contain actinides and complexing agents, 5f-element speciation in acetic acid/acetate cocktails is poorly defined. Herein, we address this problem and characterize Ac3+ and Cm3+ speciation as a function of increasing acetic acid/acetate concentrations (0.1 to 15 M, pH = 5.5). Results obtained via X-ray absorption and optical spectroscopy show the aquo ion dominated in dilute acetic acid/acetate solutions (0.1 M). Increasing acetic acid/acetate concentrations to 15 M increased complexation and revealed divergent reactivity between early and late actinides. A neutral Ac(H2O)6(1)(O2CMe)3(1) compound was the major species in solution for the large Ac3+. In contrast, smaller Cm3+ preferred forming an anion. There were approximately four bound O2CMe1− ligands and one to two inner sphere H2O ligands. The conclusion that increasing acetic acid/acetate concentrations increased acetate complexation was corroborated by characterizing (NH4)2M(O2CMe)5 (M = Eu3+, Am3+ and Cm3+) using single crystal X-ray diffraction and optical spectroscopy (absorption, emission, excitation, and excited state lifetime measurements).

Sol–gel synthesis of 2-dimensional TiO2: self-assembly of Ti–oxoalkoxy–acetate complexes by carboxylate ligand directed condensation

2-Dimensional (2D) metal oxides have many potential industrial applications including heterogeneous catalysis, water splitting, renewable energy conversion, supercapacitor applications, biomaterials, gas separation and gas storage. Herein we report a simple and scalable method for the preparation of 2D TiO2 nanostructures by reaction of titanium isopropoxide with acetic acid at 333 K in isopropanol, followed by calcination at 673 K to remove the organic ligands. Both the products and reaction intermediates have been studied using electron microscopy, X-ray diffraction, N2 physisorption, nuclear magnetic resonance, thermogravimetric analysis, and X-ray photoelectron, Raman, and infrared spectroscopy. The anisotropic condensation of the planar Ti6O4(OiPr)8(OAc)8 complex is believed to be responsible for the formation of the 2D structure, where OiPr and OAc represent isopropoxide and acetate ligands, respectively. This research demonstrates that the metal complexes are promising building blocks for desired architectures, and the self-assembly of an acetate bidentate ligand is a versatile tool for manipulating the shape of final products.

Synthesis and Spectrophotometric Properties of Sodium Metal Carboxylates

While metal carboxylates are by no means rare or inaccessible, complete characterization with notable exception of acetates is largely neglected hence a deficiency within the carboxylate literature giving rise to discrepancies within the characterization data available thus, spectroscopic properties of synthesized sodium metal carboxylates of acetic acid and myristic acid were investigated using Atomic Absorption Spectroscopy (AAS), flame photometry, FTIR spectrophotometer and UV- Visible spectrophotometry. AAS and flame photometric results showed elemental abundance of the sodium metals in the carboxylate complexes. FTIR spectra data revealed ʋCOO- absorptions at 1636 cm-1 and 1558 cm-1 for sodium acetate and sodium myristate respectively. The free acid ligands showed absorptions at 1703 cm-1 for acetic acid which shifted to 1636 cm-1 for sodium acetate. FTIR absorption of myristic acid revealed a strong absorption band at 1696 cm-1 which shifted to 1558 cm-1 in sodium myristate. The geometry of the complexes were determined by the magnitude of separation, Δʋ, which is equal to ʋaym - ʋsym,. The values of Δʋ for the synthesized sodium acetate complex was found to be 231 cm-1 and 138 cm-1 for sodium myristate indicating monodentate and bridging bidentate bonding respectively. Force constants of the carboxylates which correspond to their bond energies were found to be 1495.94 K NM-1 and 1358 K NM-1 for sodium acetate and sodium myristate, respectively. The UV- Visible analysis shows ʎ max values of 201 nm and 195 nm for sodium acetate and sodium myristate respectively, which corresponds to the absorption of the COO chromophore which is due to n-π* transition.

Influence of the copper precursor on the catalytic transformation of oleylamine during Cu nanoparticle synthesis

Copper nanoparticles prepared from copper acetylacetonate complex or acetate complex show significant differences in terms of reaction mechanism and further catalytic transformation of oleylamine.

Activation of Molecular Oxygen by a Cobalt(II) Tetra-NHC Complex*.

The first dicobalt(III) μ 2‐peroxo N‐heterocyclic carbene (NHC) complex is reported. It can be quantitatively generated from a cobalt(II) compound bearing a 16‐membered macrocyclic tetra‐NHC ligand via facile activation of dioxygen from air at ambient conditions. The reaction proceeds via an end‐on superoxo intermediate as demonstrated by EPR studies and DFT. The peroxo moiety can be cleaved upon addition of acetic acid, yielding the corresponding CoIII acetate complex going along with H2O2 formation. In contrast, both CoII and CoIII complexes are also studied as catalysts to utilize air for olefin and alkane oxidation reactions; however, not resulting in product formation. The observations are rationalized by DFT‐calculations, suggesting a nucleophilic nature of the dicobalt(III) μ 2‐peroxo complex. All isolated compounds are characterized by NMR, ESI‐MS, elemental analysis, EPR and SC‐XRD.

Enhanced dissolution rate of magnesium hydroxide via magnesia/ammonium acetate hydration system: statistical optimization and possible mechanism

AbstractBACKGROUNDThe dissolubility of magnesium hydroxide is often the main factor limiting its application effect in the environmental field, and the dissolution rate of magnesium hydroxide during its synthesis is also worthy of attention. In this paper, response surface methodology was used to synthesize magnesium hydroxide with different dissolution rates through a magnesium oxide/ammonium acetate hydration system, and the possible formation mechanism as well as dissolution performance is discussed.RESULTSCompared with the hydration temperature and time, the concentration of ammonium acetate has a more significant effect on the dissolution rate of hydrated magnesium hydroxide. A maximum dissolution rate of 43.8 ± 0.3 mmol min−1 mol−1 magnesium hydroxide could be obtained when the working factors were ammonium acetate concentration 15 g L–1, hydration temperature 75.5 °C and time 112 min.CONCLUSIONThe correlation study between structural characterization and the dissolution test shows that the complexation and replacement of acetate, in situ generation and release of ammonia appear to have some critical effects on magnesium hydroxide crystallization behaviour and induce the formation of thin, curved and defective structures. Crystals with such structures have been reported to have a higher dissolution activity. The results of this study provide an indication for screening hydration synthetic agents of high‐dissolution‐rate magnesium hydroxide. © 2020 Society of Chemical Industry (SCI)

In situ remediation of 2,4-dicholrophenoxyacetic acid herbicide using amine-functionalized imidazole coordination complexes.

Demand of clean water is always a major concern due to continuous use of toxic pesticides and herbicides to overcome food scarcity. In Asian countries, wide use of ionizable 2,4-D herbicide has worsen problem due to its less binding ability with soil and can easily contaminate drinking water that causes potential risks to humans and environment. The present research focused on synthesis of amino-factionalized coordination complexes using imidazole-based amino benzoic acid ligands for remediation of acidic 2,4-D herbicide. Coordination complexes characterized with FTIR, 1H-NMR, elemental analysis, thermogravimetric analysis, powder XRD, and BET revealed successful incorporation of functionalized groups with high thermal stability and surface area that make them suitable for adsorption experiments. Batch adsorption experiments conducted at different temperature conditions depicted the spontaneous physisorption process (- ∆G) having endothermic nature (∆H, ∆S). The removal efficiency of the amino-functionalized coordination complex is found to be higher (73%) compared to non-functionalized (35%) and acetic anhydride-functionalized coordination complex (42%). Kinetic studies supported pseudo 2nd-order kinetics with three phases of adsorption depicted by intra-particle diffusion model. Amino-functionalized complexes favored Langmuir isotherm while Freundlich isotherm is best fitted for non-functionalized complexes. The synthesized adsorbents were also proven to be effective for removal of herbicide from irrigated wastewater with average percent removal of 56% for amino functionalized, acetic anhydride functionalized (23%), and non-functionalized (20%).

Influence of Acetic Acid on the Integrity and Protectiveness by an Iron Carbonate (FeCO3) Corrosion Product Layer

The effect of undissociated acetic acid on the integrity of an iron carbonate (FeCO3) layer formed on platinum and X65 steel substrates is investigated. Experiments were conducted using buffered solutions with 0.8 mM to 5 mM undissociated acetic acid. For the platinum substrates, changes in the FeCO3 layer were monitored via in situ electrochemical quartz crystal microbalance (EQCM) measurements. This investigation was supported by performing electrochemical experiments, under comparable conditions, on the X65 steel specimens, linking the integrity of FeCO3 layer to its corrosion protection effect. The EQCM measurements revealed that the addition of acetic acid, at all concentrations tested here, caused partial dissolution of the FeCO3 layer. The dissolution occurred selectively, with the outer layer dissolving first, leaving behind an inner FeCO3 layer at the end of the immersion experiment. The electrochemical results revealed that introducing the acetic acid caused a sudden increase in the corrosion rate, which over time returned to a lower value similar in magnitude to that seen before addition of the acetic acid. This was attributed to the protection provided by the inner FeCO3 layer, which was only mildly affected by the addition of acetic acid and was able to repair over time. It was proven that the dissolution of the protective FeCO3 layer in the presence of acetic acid was not due to a small pH change but rather due to the formation of ferrous acetate complexes and changes in ionic strength, which decreases the FeCO3 saturation values.

Cover Feature: Acetylacetonate and Acetate Complexes of Nickel(II) Catalyse the Air Oxidation of Phosphines (Eur. J. Inorg. Chem. 44/2020)

Cover Feature: Acetylacetonate and Acetate Complexes of Nickel(II) Catalyse the Air Oxidation of Phosphines (Eur. J. Inorg. Chem. 44/2020)

Front Cover: Asymmetric Synthesis of Multi‐substituted Prolines via a Catalytic 1,3‐Dipolar Cycloaddition Using a Monocationic ZnIIOAc Complex of a Chiral Bisamidine Ligand, Naph‐diPIM‐dioxo‐R (ChemCatChem 22/2020)

The Front Cover shows a highly efficient catalytic enantioselective 1,3-dipolar cycloaddition of tridentate-type α-imino esters and acrylates. In their Communication, I. N. Chaithanya Kiran et al. explain the catalyst's design concept and its performance for the reaction. The catalyst is a monocationic zinc acetate complex of a chiral bisamidine-type bidentate ligand. An anionic acetate ligand of the Lewis acidic Zn complex acts as a Brønsted base to facilitate a smooth intramolecular deprotonation to generate an imino N,O-cis-Zn enolate. The oxygen atoms of two dioxolanes of the ligand form a C2 chiral scaffold, in which the Zn enolate position is well controlled by a non-bonding n-π* interaction. The catalyst shows high activity, diastero-/enantio-/regio-selectivity, productivity, and broad generality. This reaction provides a path for the synthesis of pyrrolidine-containing chiral bioactive compounds, ligands and organocatalysts. More information can be found in the Communication by I. N. Chaithanya Kiran et al.

A Monocationic Zn(II) Acetate Complex of a Chiral Bisamidine Dioxolane Ligand, Naph-diPIM-dioxo-R, for the Asymmetric 1,3-Dipolar Cycloaddition of Tridentate α-Substituted α-Imino Esters and Acrylates to Multi-Substituted Prolines: Importance of an n-π* Interaction for High Enantioselectivity

Abstract A monocationic Zn(II) acetate complex of a C2-chiral bisamidine-type sp2N bidentate ligand (LR) possessing two dioxolane oxygen n orbitals in the reaction site catalyzes, without the use of an external base, a highly efficient asymmetric 1,3-dipolar cycloaddition (1,3-DC) of tridentate α-substituted α-imino esters with acrylates, attaining up to >99:1 enantiomeric ratio with perfect regio- and diastereo-selectivities. A catalyst loading of 0.1 mol% is generally acceptable to furnish various chiral multi-substituted prolines. Both (S)-α-imino ester and the R enantiomer show a high level of enantioselectivity. An overall picture of the present 1,3-DC has been revealed via analyses of substrate structure/reactivity/selectivity relationships, NMR, MS, X-ray diffraction, 12C/13C isotope effects, rate law, and kinetics. The first success in the high performance 1,3-DC is ascribed to i) a Brønsted base/Lewis acid synergistic effect of [Zn(OAc)LR]OTf (R cat); ii) the existence of the n orbital, which determines the position of the intermediary N,O-cis-Zn enolate (dipole) by an n-π* non-bonding attractive interaction between the oxygen atom in LR and the C=N moiety of the dipole; and iii) utilization of chelatable α-imino esters capturing Zn(II) as a tridentate ligand. A 12C/13C analysis has clarified that a stepwise 1,3-DC mechanism is operating.

Crystal structure, thermal analyses, and acetate binding properties in Zinc(II) complex of a urea-functionalized pyridyl ligand

A zinc(II) acetate complex with a urea-functionalized pyridyl ligand, [ZnL2(OAc)2]·2H2O (1) (L = N-(4-chlorophenyl)-N'-(4-pyridyl)urea), has been synthesized by the reaction of L with Zn(OAc)2·2H2O under water-containing condition. X-ray single-crystal diffraction analyses reveal that 2-D sheetlike network structure is formed by the urea N−H×××Npyridyl interactions and C–H···O interactions in the free ligand L. Complex 1 features 3-D hydrogen bonded network formed by intermolecular N−H×××O hydrogen bonds and O−H×××O hydrogen bonds involving urea groups, acetate anions and bridged water molecules. The hydrogen bonds play an important role in stabilizing the supramolecular structures. Thermal gravity analyses are used to investigate the thermal stabilities of L and 1, and the apparent activation energy (Ea) of the decompositions are also calculated, and the results indicate that the main decomposition of L needs higher apparent activation energy values Ea than that of 1. The acetate binding properties of L in solution are also evaluated by Ultraviolet-Visible (UV-Vis) spectroscopy. CCDC: 1506202, L; 1506203, 1.

Acetylacetonate and Acetate Complexes of Nickel(II) Catalyse the Air Oxidation of Phosphines

The polymeric complex trans‐[Ni(acac)2(µ2‐dppe)]n·2MeCN {1a, dppe = 1,2‐ethylenebis(diphenylphosphine)} is sometimes transiently deposited from the reaction of [Ni(acac)2] with dppe in MeCN prior to its facile onwards air oxidation to final crystallization of a doubly‐oxygenated relative, cis‐[Ni(acac)2(µ2‐dppeO2)]n {2, dppeO2 = 1,2‐ethylenebis(diphenylphosphineoxide)}. A similar unsolvated phase of the initial polymer, trans‐[Ni(acac)2(µ2‐dppe)]n (1b), can be isolated from toluene. The oxidation of dppe by O2 is catalytic and dppeO2 was isolated in close to stoichiometric yields from solutions containing 5 % Ni(acac)2 relative to dppe. The reaction rate slows after a few turnovers due to inhibition by the product. The relative yields of dppeO2 are higher than those from catalytic air oxidation of methyldiphenylphosphine and triphenylphosphine and we speculate that a pathway for this reaction involves a dimetallic cooperativity enabled specifically by dppe.