Advanced ethylene-absorbing and cushioning depending on the 3D porous-structured fruit packaging: Toward polyurethane foam manipulation using zein and soybean oil polyol substrates.

Fruits are essential sources of nutrients in our daily diet; however, their spoilage is often intensified by mechanical damage and the ethylene phytohormone, resulting in significant economic losses and exacerbating hunger issues. To address these challenges, this study presented a straightforward in situ synthesis protocol for producing Z/SOPPU foam, a 3D porous-structured fruit packaging. This innovative packaging material offered advanced ethylene-adsorbing and cushioning capabilities achieved through stirring, heating, and standing treatments. The results demonstrated that the Z/SOPPU foam, with its porous structure, served as an excellent packaging material for fruits, maintaining the intact appearance of tomatoes even after being thrown 72 times from a height of 1.5 m. Additionally, it exhibited desirable hydrophobicity (contact angle of 114.31 ± 0.82°), degradability (2.73 ± 0.88 % per 4 weeks), and efficient ethylene adsorption (adsorption rate of 13.2 ± 1.7 mg/m3/h). These remarkable characteristics could be attributed to the unique 3D micron-porous configuration, consisting of soybean oil polyol polyurethane foam for mechanical strain cushioning and zein for enhanced ethylene adsorption efficiency. Overall, this research offers an effective and original approach to the rational design and fabrication of advanced bio-based fruit packaging.

Insights into the hydrolysis/alcoholysis/ammonolysis mechanisms of ethylene naphthalate dimer using density functional theory (DFT) method.

Hydrolysis, alcoholysis and ammonolysis are viable routes for the efficient degradation and recycling of polyethylene naphthalate (PEN) plastic waste. Various possible hydrolysis/alcoholysis/ammonolysis reaction pathways for the degradation mechanism of the ethylene naphthalate dimer were investigated using the density functional theory (DFT) B3P86/6-31++G(d,p). To determine the thermodynamic and kinetic parameters, geometric structure optimization and frequency calculation were performed on a range of intermediates, transition states, and products associated with the reaction. The calculation results show that the highest energy barrier of the main element reaction step in hydrolysis is about 169.0 kJ/mol, the lowest is about 151.0 kJ/mol for ammonolysis, and the second is about 155.0 kJ/mol for alcoholysis. The main hydrolysis products of the ethylene naphthalate dimer are 2,6-naphthalenedicarboxylic acid and ethylene glycol; the main products of alcoholysis are dimethyl naphthalene-2,6-dicarboxylate and ethylene glycol, and the main products of ammonolysis are naphthalene-2,6-dicarboxamide and ethylene glycol. Furthermore, in the process of ethylene naphthalate dimer hydrolysis/alcoholysis/ammonolysis, the decomposition reaction in the NH3 atmosphere is better than that in methanol, and the reaction in CH3OH is better than that in the H2O molecular environment, and the increase in reaction temperature can increase its spontaneity. Our study presents the molecular mechanism of PEN hydrolysis/alcoholysis/ammonolysis and provides a reference for studying the degradation of other plastic wastes.

One-pot co-crystallized hexanal-loaded ZIF-8/quaternized chitosan film for temperature-responsive ethylene inhibition and climacteric fruit preservation.

Controlling ethylene production and microbial infection are key factors to prolong the shelf life of climacteric fruit. Herein, a nanocomposite film, hexanal-loaded ZIF-8/CS (HZCF) with "nano-barrier" structure, was developed by a one-pot co-crystallized of ZIF-8 in situ growth on quaternized chitosan (CS) and encapsulation of hexanal into ZIF-8 via microporous adsorption. The resultant film realized the temperature responsive release of hexanal via the steric hindrance and hierarchical pore structure as "nano-barrier", which can inhibit ethylene production in climacteric fruit on demand. Based on this, the maximum ethylene inhibition rate of HZCF was up to 52.6 %. Meanwhile, the film exhibits excellent antibacterial, mechanical, UV resistance and water retention properties, by virtue of the functional synergy between ZIF-8 and CS. Contributed to the multifunctional features, HZCF prolonged the shelf life of banana and mango for at least 16 days, which is 8 days longer than that of control fruit. More strikingly, HZCF is washable and biodegradable, which is expected to replace non-degradable plastic film. Thus, this study provides a convenient novel approach to simplify the encapsulation of active molecule on metal-organic frameworks (MOFs), develops a packaging material for high-efficient freshness preservation, and helps to alleviate the survival crisis caused by food waste.

Steric Perturbation of the Grob-like Final Step of Ethylene-Forming Enzyme Enables 3-Hydroxypropionate and Propylene Production.

Ethylene-forming enzyme (EFE) is an iron(II)-dependent dioxygenase that fragments 2-oxoglutarate (2OG) to ethylene (from C3 and C4) and 3 equivs of carbon dioxide (from C1, C2, and C5). This major ethylene-forming pathway requires l-arginine as the effector and competes with a minor pathway that merely decarboxylates 2OG to succinate as it oxidatively fragments l-arginine. We previously proposed that ethylene forms in a polar-concerted (Grob-like) fragmentation of a (2-carboxyethyl)carbonatoiron(II) intermediate, formed by the coupling of a C3-C5-derived propion-3-yl radical to a C1-derived carbonate coordinated to the Fe(III) cofactor. Replacement of one or both C4 hydrogens of 2OG by fluorine, methyl, or hydroxyl favored the elimination products 2-(F1-2/Me/OH)-3-hydroxypropionate and CO2 over the expected olefin or carbonyl products, implying strict stereoelectronic requirements in the final step, as is known for Grob fragmentations. Here, we substituted active-site residues expected to interact sterically with the proposed Grob intermediate, aiming to disrupt or enable the antiperiplanar disposition of the carboxylate electrofuge and carbonate nucleofuge required for concerted fragmentation. The bulk-increasing A198L substitution barely affects the first partition between the major and minor pathways but then, as intended, markedly diminishes ethylene production in favor of 3-hydroxypropionate. Conversely, the bulk-diminishing L206V substitution enables propylene formation from (4R)-methyl-2OG, presumably by allowing the otherwise sterically disfavored antiperiplanar conformation of the Grob intermediate bearing the extra methyl group. The results provide additional evidence for a polar-concerted ethylene-yielding step and thus for the proposed radical-polar crossover via substrate-radical coupling to the Fe(III)-coordinated carbonate.

Machine Learning Models for Predicting Zirconocene Properties and Barriers.

Zr metallocenes have significant potential to be highly tunable polyethylene catalysts through modification of the aromatic ligand framework. Here we report the development of multiple machine learning models using a large library (>700 systems) of DFT-calculated zirconocene properties and barriers for ethylene polymerization. We show that very accurate machine learning models are possible for HOMO-LUMO gaps of precatalysts but the performance significantly depends on the machine learning algorithm and type of featurization, such as fingerprints, Coulomb matrices, smooth overlap of atomic positions, or persistence images. Surprisingly, the description of the bonding hapticity, the number of direct connections between Zr and the ligand aromatic carbons, only has a moderate influence on the performance of most models. Despite robust models for HOMO-LUMO gaps, these types of machine learning models based on structure connectivity type features perform poorly in predicting ethylene migratory insertion barrier heights. Therefore, we developed several relatively robust and accurate machine learning models for barrier heights that are based on quantum-chemical descriptors (QCDs). The quantitative accuracy of these models depends on which potential energy surface structure QCDs were harvested from. This revealed a Hammett-type principle to naturally emerge showing that QCDs from the π-coordination complexes provide much better descriptions of the transition states than other potential-energy structures. Feature importance analysis of the QCDs provides several fundamental principles that influence zirconocene catalyst reactivity.

Recent Advances in Synthesis of Non-Alternating Polyketone Generated by Copolymerization of Carbon Monoxide and Ethylene.

The copolymers of carbon monoxide (CO) and ethylene, namely aliphatic polyketones (PKs), have attracted considerable attention due to their unique property and degradation. Based on the arrangement of the ethylene and carbonyl groups in the polymer chain, PKs can be divided into perfect alternating and non-perfect alternating copolymers. Perfect alternating PKs have been previously reviewed, we herein focus on recent advances in the synthesis of PKs without a perfect alternating structure including non-perfect alternating PKs and PE with in-chain ketones. The chain structure of PKs, catalytic copolymerization mechanism, and non-alternating polymerization catalysts including phosphine-sulfonate Pd, diphosphazane monoxide (PNPO) Pd/Ni, and phosphinophenolate Ni catalysts are comprehensively summarized. This review aims to enlighten the design of ethylene/CO non-alternating polymerization catalysts for the development of new polyketone materials.

An exact and vigorous kinetic Monte Carlo simulation to determine the properties of bimodal HDPE synthesized with a dual-site metallocene catalyst.

A vigorous and progressed Monte Carlo strategy was developed to precisely simulate the ethylene and 1-butene copolymerization within the presence of hydrogen by dual-site metallocene catalyst. The results showed up that the ethylene and 1-butene consumption rates at the second catalyst site were approximately 5 times higher than at the first site, and hydrogen transfer rates at the first catalyst site were over 3 times more rapid than at the second site. It was found that the most elevated molar percentage of 1-butene inside the copolymers synthesized from the second site was around 12% and within the copolymers gotten from the first site was around 2%. At a steady hydrogen concentration, with 8 times increase in the 1-butene concentration within the initial feed, the overall weight average molecular weight (M‾w) and an overall number average molecular weight (M‾n) extended by approximately 50% and 40%, respectively. Besides, at a consistent 1-butene concentration, with 8 times increase in the concentration of hydrogen, M‾w and M‾n diminished by approximately 18% and 22%, separately. Due to the synthesis of two groups of chains with distinct molecular weights, the overall dispersity (D) was slightly higher than the dispersity resulting from each catalyst site (1.5-2.1). With increasing 1-butene concentrations, the overall bimodal molecular weight distribution (MWD) widened, and the peak sizes grew smaller and moved towards higher molecular weights. As hydrogen concentration increased, peaks became taller and move toward shorter chain lengths. It was observed that the first site created chain lengths between 102 and 103 while the second site generated chain lengths between 102 and 106. As the concentration of 1-butene was increased in the initial feed, the number of short chain branching per 1000 carbon atoms (SCB/1000C) increased from 10 to 50. Compared to the first site, there were 5 times as many SCBs at the chains produced from the second site. By diminishing the ratio of ethylene to 1-butene, the melt index (MI) tended towards smaller numbers (0.2≤MI≤2). With an increase in the ratio of ethylene to 1-butene and ethylene to hydrogen, the weight fraction of crystals raised from 67.4 to 69.5% and diminished from 71 to 69.5%, respectively. At last, increasing the temperature led to a diminish in molecular weight, a narrowing of the bimodal MWD, an increment within the thickness and weight fraction of crystals, and an increment within the density of HDPE.

Unraveling the comonomer distribution in ethylene - vinyl ester terpolymers through liquid chromatography with infrared detection.

Polyolefins are the most commercially relevant polymers by volume. A readily available feedstock and their tailor-made microstructure allow to adapt polyolefins to many fields of application. Important molecular design features of olefin copolymers are the molar mass distribution (MMD) with the corresponding average values, comonomer type, chemical composition distribution (CCD) with the corresponding average and the tacticity distribution (TD). Advanced separation techniques i.e., high-temperature gel permeation chromatography (HT-GPC) as well as its hyphenation with high-temperature high performance liquid chromatography (HT-HPLC) in the form of high-temperature two-dimensional liquid chromatography (HT 2D-LC) have been successfully applied in this work. This allowed to deeply analyze the molecular heterogeneities of complex polyolefin terpolymers consisting of ethylene, vinyl acetate and branched vinyl ester monomers. By using filter-based infrared detection, the capabilities of HT-GPC are further extended so that the distribution of methyl- and carbonyl groups could be obtained along the molar mass axis. Using porous graphitic carbon (PGC) as a stationary phase for HT-HPLC separation provided information about the CCD of these complex polyolefins from experimental data as part of the hyphenated approach of HT 2D-LC. The latter revealed the full MMD x CCD distribution function, which is the key for a comprehensive analysis of the bivariate molecular structure of the polyolefin terpolymers.

Can an external electric field switch between ethylene formation and L-arginine hydroxylation in the ethylene forming enzyme?

The non-heme Fe(II) and 2-oxoglutarate (2OG) dependent ethylene-forming enzyme (EFE) catalyzes both ethylene generation and L-Arg hydroxylation. Despite experimental and computational progress in understanding the mechanism of EFE, no EFE variant has been optimized for ethylene production while simultaneously reducing the L-Arg hydroxylation activity. In this study, we show that the two L-Arg binding conformations, associated with different reactivity preferences in EFE, lead to differences in the intrinsic electric field (IntEF) of EFE. Importantly, we suggest that applying an external electric field (ExtEF) along the Fe-O bond in the EFE·Fe(III)·OO-˙·2OG·L-Arg complex can switch the EFE reactivity between L-Arg hydroxylation and ethylene generation. Furthermore, we explored how applying an ExtEF alters the geometry, electronic structure of the key reaction intermediates, and the individual energy contributions of second coordination sphere (SCS) residues through combined quantum mechanics/molecular mechanics (QM/MM) calculations. Experimentally generated variant forms of EFE with alanine substituted for SCS residues responsible for stabilizing the key intermediates in the two reactions of EFE led to changes in enzyme activity, thus demonstrating the key role of these residues. Overall, the results of applying an ExtEF indicate that making the IntEF of EFE less negative and stabilizing the off-line binding of 2OG is predicted to increase ethylene generation while reducing L-Arg hydroxylation.

A Bridge too Far? Comparison of Transition Metal Complexes of Dibenzyltetraazamacrocycles with and without Ethylene Cross-Bridges: X-ray Crystal Structures, Kinetic Stability, and Electronic Properties.

Tetraazamacrocycles, cyclic molecules with four nitrogen atoms, have long been known to produce highly stable transition metal complexes. Cross-bridging such molecules with two-carbon chains has been shown to enhance the stability of these complexes even further. This provides enough stability to use the resulting compounds in applications as diverse and demanding as aqueous, green oxidation catalysis all the way to drug molecules injected into humans. Although the stability of these compounds is believed to result from the increased rigidity and topological complexity imparted by the cross-bridge, there is insufficient experimental data to exclude other causes. In this study, standard organic and inorganic synthetic methods were used to produce unbridged dibenzyl tetraazamacrocycle complexes of Co, Ni, Cu, and Zn that are analogues of known cross-bridged tetraazamacrocycles and their transition metal complexes to allow direct comparison of molecules that are identical except for the cross-bridge. The syntheses of the known tetraazamacrocycles and the new transition metal complexes were successful with high yields and purity. Initial chemical characterization of the complexes was conducted by UV-Visible spectroscopy, while cyclic voltammetry showed more marked differences in electronic properties from bridged versions. Direct comparison studies of the unbridged and bridged compounds' kinetic stabilities, as demonstrated by decomposition using high acid concentration and elevated temperature, showed that the cyclen-based complex stability did not benefit from cross-bridging. This is likely due to poor complementarity with the Cu2+ ion while cyclam-based complexes benefited greatly. We conclude that ligand-metal complementarity must be maintained in order for the topological and rigidity constraints imparted by the cross-bridge to contribute significantly to complex robustness.

Brønsted acid catalyzed annulations of ketene dithioacetals: synthesis of 3-aryl coumarins and indenes.

PTSA-catalyzed divergent synthetic routes toward 3-aryl coumarins and indenes have been developed using ketene dithioacetals. These transformations are transition-metal and oxidant free, proceed under mild conditions, and provide expeditious access to these important structural motifs.

Over-expression of GGP1 and GPP genes enhances ascorbate content and nutritional quality of tomato.

L-Ascorbic acid (AsA), a strong antioxidant, serves as an enzyme cofactor and redox status marker, modulating a plethora of biological processes. As tomato commercial varieties and hybrids possess relatively low amounts of AsA, the improvement of fruit AsA represents a strategic goal for enhanced human health. Previously, we have suggested that GDP-L-Galactose phosphorylase (GGP) and L-galactose-1-phosphate phosphatase (GPP) can serve as possible targets for AsA manipulation in tomato (Solanum lycopersicon L.) fruit. To this end, we produced and evaluated T3 transgenic tomato plants carrying these two genes under the control of CaMV-35S and two fruit specific promoters, PPC2 and PG-GGPI. The transgenic lines had elevated levels of AsA, with the PG-GGP1 line containing 3-fold more AsA than WT, without affecting fruit characteristics. Following RNA-Seq analysis, 164 and 13 DEGs were up- or down-regulated, respectively, between PG-GGP1 and WT pink fruits. PG-GGP1 fruit had a distinct number of up-regulated transcripts associated with cell wall modification, ethylene biosynthesis and signaling, pollen fertility and carotenoid metabolism. The elevated AsA accumulation resulted in the up regulation of AsA associated transcripts and alternative biosynthetic pathways suggesting that the entire metabolic pathway was influenced, probably via master regulation. We show here that AsA-fortification of tomato ripe fruit via GGP1 overexpression under the action of a fruit specific promoter PG affects fruit development and ripening, reduces ethylene production, and increased the levels of sugars, and carotenoids, supporting a robust database to further explore the role of AsA induced genes for agronomically important traits, breeding programs and precision gene editing approaches.

Generation of 4'-Carbon Radicals via 1,5-Hydrogen Atom Transfer for the Synthesis of Bridged Nucleosides.

The rapid and facile generation of 4'-carbon radicals from oxime imidates of nucleosides via 1,5-hydrogen atom transfer induced by iminyl radicals was developed. The cyclization of 4'-carbon radicals with olefins, followed by the hydrolysis of imidate residues, provided various 2'-O,4'-C- and 3'-O,4'-C-bridged nucleosides. This operationally simple approach can be applied to the few-step syntheses of 6'S-methyl-2'-O,4'-C-ethylene-bridged 5-methyluridine (6'S-Me-ENA-T) and S-constrained ethyl-bridged 5-methyluridine (S-cEt-T).

Customizing Polymers by Controlling Cation Switching Dynamics in Non-Living Polymerization.

Controlling the chain growth process in non-living polymerization reactions is difficult because chain termination typically occurs faster than the time it takes to apply an external trigger. To overcome this limitation, we have developed a strategy to regulate non-living polymerizations by exploiting the chemical equilibria between a metal catalyst and secondary metal cations. We have prepared two nickel phenoxyphosphine-polyethylene glycol variants, one with 2-methoxyphenyl (Ni1) and another with 2,6-dimethoxyphenyl (Ni2) phosphine substituents. Ethylene polymerization studies using these complexes in the presence of alkali salts revealed that chain growth is strongly dependent on electronic effects, whereas chain termination is dependent on both steric and electronic effects. By adjusting the solvent polarity, we can favor polymerizations via non-switching or dynamic switching modes. For example, in a 100:0.2 mixture of toluene/diethyl ether, reactions of Ni1 and both Li+ and Na+ cations in the presence of ethylene yielded bimodal polymers with different relative fractions depending on the Li+/Na+ ratio used. In a 98:2 mixture of toluene/diethyl ether, reactions of Ni2 and Cs+ in the presence of ethylene generated monomodal polyethylene with dispersity <2.0 and increasing molecular weight as the amount of Cs+ added increased. Solution studies by NMR spectroscopy showed that cation exchange between the nickel complexes and alkali cations in 98:2 toluene/diethyl ether is fast on the NMR time scale, which supports our proposed dynamic switching mechanism.

Solid-State Emission and Aggregate Emission of Aroyl- S,N-Ketene Acetals Are Controlled and Tuned by Their Substitution Pattern.

Aroyl-S,N-ketene acetals are a novel highly diverse class of aggregation-induced emission fluorogens (AIEgens) with a plethora of interesting properties. An expanded compound library of more than 110 dyes set the stage for the first qualitative control and tuneability of all aspects of their photophysical properties. The interplay of substituents not only allows tuning and prediction of the emission color, but also of the intensity, and quantum yields both in solids and in the aggregated state; these can be rationalized by scrutinizing intermolecular interactions in the crystalline solid state.

Catalytic deconstruction of waste polyethylene with ethylene to form propylene.

The conversion of polyolefins to monomers would create a valuable carbon feedstock from the largest fraction of waste plastic. However, breakdown of the main chains in these polymers requires the cleavage of carbon-carbon bonds that tend to resist selective chemical transformations. Here, we report the production of propylene by partial dehydrogenation of polyethylene and tandem isomerizing ethenolysis of the desaturated chain. Dehydrogenation of high-density polyethylene with either an iridium-pincer complex or platinum/zinc supported on silica as catalysts yielded dehydrogenated material containing up to 3.2% internal olefins; the combination of a second-generation Hoveyda-Grubbs metathesis catalyst and [PdP(tBu)3(µ-Br)]2 as an isomerization catalyst selectively degraded this unsaturated polymer to propylene in yields exceeding 80%. These results show promise for the application of mild catalysis to deconstruct otherwise stable polyolefins.

Synthesis of diverse spiro-imidazo pyridine-indene derivatives via acid-promoted annulation reaction of bindone and heterocyclic ketene aminals.

A new multi-component reaction for the synthesis of novel and diverse spiro-imidazo pyridine-indene derivatives named spiro[imidazo[1,2-a]indeno[2,1-e]pyridine-5,1'-indene and indenylidene-1H-spiro[imidazo[1,2-a]pyridine-7,1'-indene was successfully developed by the reaction between heterocyclic ketene aminals (generated from 1,1-bis(methylthio)-2-nitro ethylene and diamine) and [1,2'-biindenylidene]-1',3,3'-trione (bindone) (in situ generated from self-condensation of 1,3-indandion) by using malononitrile as a promoter or as one of the precursors respectively in the presence of p-TSA as the acid catalyst in EtOH as reaction medium under reflux conditions. Depending on whether the reaction is single-step or two-step, malononitrile can act as a promoter or reactant. The convenient one-pot operation, straightforward isolation without using additional purification methods, and the use of a variety of diamines and cysteamine hydrochloride causing a variety of structural products are attractive aspects of the present approach. The synthesized bindone and final product contains active methylene and this active site can be involved in further reactions to synthesize more complex heterocycles.

Effect of lipids complexes on controlling ethylene gas release from V-type starch.

In this study, the effects of n-decanoic acid (n-CA) or coconut oil (CCN) on the release of ethylene from V-type starch (VS) were investigated. Results of differential scanning calorimetry showed that adding n-CA or CCN into VS generated a starch-lipid complex. Results of scanning electron microscopy and confocal laser scanning microscopy indicated that VS granules aggregated but oil films appeared on the surface of the VS aggregates when oil was added. The addition of n-CA or CCN effectively delayed the release of ethylene in VS, and the deceleration effect gradually became obvious with the increase in oil addition. These results suggest that the formation of starch-lipid complexes, the aggregation of starch granules, and the presence of oil films play important roles in slowing down the release of ethylene.

Convenient, nondestructive monitoring and sustained-release of ethephon/chitosan film for on-demand of fruit ripening.

The microstructure changes (such as micro defects and free volume, etc.) is a deep factor that determines the sustained release behavior of polymer film. However, there are few reports exploring the micro defects of sustained-release materials. Herein, we develop a facile method to non-destructive monitoring and sustained-release ethylene within chitosan. The comprehensive means of positron annihilation lifetime spectroscopy, atomic force microscopy and Raman spectrums are performed together to study the microstructures change of ethylene sustained-release and its mechanism. When ethylene is in chitosan film, it shows good ripening performance and mechanical properties. The sustained-release ethylene improves its bioavailability and can control the fruit-ripening on-demand. More importantly, the microstructural changes of cavities have a significant impact on the sustained release of ethylene, due to the creation of cavities, the free volume of positrons undergoes a process of increasing from less to more and then gradually decreasing, reaching a maximum at 120 h. Furthermore, the ethephon/chitosan film could on-demand control the ripening time of mangoes and bananas. Therefore, this research presents a comprehensive means to study of microstructure change monitoring and controllable sustained release, and provides the possibility to solve the problem of on-demand ripening of fruit and reducing pesticide residue.

Tungstacyclopentane Ring Contraction Yields Olefin Metathesis Catalysts.

Exposure of a solution of the square pyramidal tungstacyclopentane complex W(NAr)(OSiPh3)2(C4H8) (Ar = 2,6-i-Pr2C6H3) to ethylene at 22 °C in ambient (fluorescent) light slowly leads to the formation of propylene and the square pyramidal tungstacyclobutane complex W(NAr)(OSiPh3)2(C3H6). No reaction takes place in the dark, but the reaction is >90% complete in ∼15 min under blue LED light (∼450 nm λmax). The intermediates are proposed to be (first) an α methyl tungstacyclobutane complex (W(NAr)(OSiPh3)2(αMeC3H5)), and then from it, a ß methyl version. The TBP versions of each can lose propylene and form a methylene complex, and in the presence of ethylene, the unsubstituted tungstacyclobutane complex W(NAr)(OSiPh3)2(C3H6). The W-Cα bond in an unobservable TBP W(NAr)(OSiPh3)2(C4H8) isomer in which the C4H8 ring is equatorial is proposed to be cleaved homolytically by light. A hydrogen atom moves or is moved from C3 to the terminal C4 carbon in the butyl chain as the bond between W and C3 forms to give the TBP α methyl tungstacyclobutane complex. Essentially, the same behavior is observed for W(NCPh3)(OSiPh3)2(C4H8) as for W(NAr)(OSiPh3)2(C4H8), except that the rate of consumption of W(NCPh3)(OSiPh3)2(C4H8) is about half that of W(NAr)(OSiPh3)2(C4H8). In this case, an α methyl-substituted tungstacyclobutane intermediate is observed, and the overall rate of formation of W(NCPh3)(OSiPh3)2(C3H6) and propylene from W(NCPh3)(OSiPh3)2(C4H8) is ∼20 times slower than in the NAr system. These results constitute the first experimentally documented examples of forming a metallacyclobutane ring from a metallacyclopentane ring (ring contraction) and establish how metathesis-active methylene and metallacyclobutane complexes can be formed and reformed in the presence of ethylene. They also raise the possibility that ambient light could play a role in some metathesis reactions that involve ethylene and tungsten-based imido alkylidene olefin metathesis catalysts, if not others.