Isolable Spirocyclic Silylone: π-Delocalized Spiro[3.3]heptasila-2,6-diylidone.

Strained cyclic tetrylones are important synthons due to various synthetic applications. Connecting two cyclic tetrylone rings through a single shared quaternary group 14 element atom to form a spirocyclic molecule has been unexplored both theoretically and experimentally. The formation of a spirocyclic motif has been a synthetic challenge. In contrast, the reaction of amidinato disilicon(I) 1, (Me3P)2SiCl4, and KC8 afforded π-delocalized spiro[3.3]heptasila-2,6-diylidone2 and tetrasilacyclobutadiene byproducts 3 and 4. Compound 2 is the smallest spirocyclic tetrylone derivative, which is composed of a σ-type lone pair and delocalized π bond in each all-silicon spirocyclic ring. The electronic property is supported by its coordination with a W(CO)5 moiety.

Tetrakis(N-heterocyclic Carbene)-Diboron(0): Double Single-Electron-Transfer Reactivity.

The use of 1,3,4,5-tetramethylimidazol-2-ylidene (IMe) to coordinate with diatomic B2 species afforded a tetrakis(N-heterocyclic carbene)-diboron(0) [(IMe)2B-B(IMe)2] (2). The singly bonded B2 moiety therein possesses a valence electronic configuration 1σg21πu21πg*2 with four vacant molecular orbitals (1σu*, 2σg, 1πu', 1πg'*) coordinated with IMe. Its unprecedented electronic structure is analogous to the energetically unfavorable planar hydrazine with a D2h symmetry. The two highly reactive πg* antibonding electrons enable double single-electron-transfer (SET) reactivity in small-molecule activation. Compound 2 underwent a double SET reduction with CO2 to form two carbon dioxide radical anions CO2•-, which then reduced pyridine to yield a carboxylated pyridine reductive coupling dianion [O2CNC5(H)5-C5(H)5NCO2]2- and converted compound 2 to the tetrakis(N-heterocyclic carbene)-diborene dication [(IMe)2B═B(IMe)2]2+ (32+). This is a remarkable transition-metal-free SET reduction of CO2 without ultraviolet/visible (UV/vis) light conditions.

Reactivity Analysis of the [2 + 2] Cycloaddition between Group-6 ≡ Group-14 Triple-Bonded Complexes and Acetylene: Insights from Theoretical Studies.

Theoretical examinations of reactivity for the formal [2 + 2] cycloaddition of Me-C≡C-Ph to Group-6(G6)≡Group-14(G14) triple-bonded organometallic complexes have been carried out using the M06-2X-D3/def2-TZVP level of theory. Our theoretical findings suggest that Me-C≡C-Ph can undergo adduct formation with all G6≡Si complexes, resulting in the generation of four-membered ring structures. However, among the W≡Group-14 complex reactants, only W≡Si-based, W≡Ge-based, and W≡Sn-based organometallic molecules are capable of undergoing a [2 + 2] cycloaddition reaction with Me-C≡C-Ph. Based on energy decomposition analysis, our theoretical investigations demonstrate that the bonding mechanism in such [2 + 2] cycloaddition reactions involves the creation of two dative bonds between singlet fragments (the donor-acceptor model), as opposed to two electron-sharing bonds between triplet fragments. In addition, the examinations based on the activation strain model indicate that the activation barrier of the [2 + 2] cycloaddition reaction is predominantly governed by the geometric deformation energy of the two reactants (G6≡G14-Rea and Me-C≡C-Ph). Our research using the M06-2X method shows that the barrier heights of [2 + 2] cycloaddition reactions between Me-C≡C-Ph and G6≡Si-Rea are dependent on the geometric changes occurring in both fragments during the transition states, consistent with Hammond's postulate.

Computational insights into CO2 binding reactions by intramolecular geminal group-IV+/phosphorus- and zirconium+/group-15-based frustrated Lewis pairs.

In order to reduce global warming, there is growing interest in the design of frustrated Lewis pair (FLP) molecules for CO2 capture. This research aims to investigate the influence of group IV (M) or group 15 (G15) elements on the reactivity of intramolecular geminal M+/G15-based frustrated Lewis pair (FLP) molecules in CO2 capture. Theoretical findings suggest that M+/P-FLP, Zr+/P-FLP, Zr+/As-FLP, and Zr+/Sb-FLP can readily undergo CO2 capture reactions without difficulty. Furthermore, Zr+/As-FLP and Zr+/Sb-FLP are predicted to undergo reversible CO2 binding reactions. Interestingly, our theoretical results suggest that the M-P bond length in isolated M+/P-FLP can serve as a criterion for assessing the free activation and free reaction energy of CO2 binding. To investigate the physical factors governing the reactivity trends for the capture of CO2 reactions by intramolecular geminal M+/G15-FLP, we employed frontier molecular orbital theory, energy decomposition analysis in conjunction with natural orbitals and chemical valence, and the activation strain model. Our theoretical information can assist experimental chemists in applying key factors in the design and synthesis of novel intramolecular geminal M+/G15-FLP molecules.

Enhanced salt tolerance of euryhaline tadpoles depends on increased Na+, K+-ATPase expression after salinity acclimation.

Understanding physiological responses and osmoregulatory mechanisms for dealing with salinity stress is essential to clarify how amphibians living in coastal areas adapt to fluctuating salinity levels. Euryhaline species are rare among reported tadpole species inhabiting saline habitats, and few studies addressed the osmoregulatory mechanisms. We quantified the effects of salinity acclimation on survival, osmolality, water content, ion concentration, and gill Na+, K+-ATPase (NKA) expression of euryhaline tadpoles of Fejervarya cancrivora, to examine time-course changes of osmoregulatory responses of tadpoles subjected to salinity stress and how osmoregulatory mechanisms were involved in the process. Acclimation to 10 ppt for 24 h increased tadpole survival of F. cancrivora in 15 ppt, and it activated osmoregulatory mechanisms such as increase in NKA expression, which enabled them to maintain a stable osmolality below that of the surrounding media, to reach lower sodium and chloride concentrations of body fluid, and to modulate dehydration at higher salinities. The minimum required acclimation period is shorter than that reported previously on this species and non-euryhaline tadpoles. This study highlights that these physiological mechanisms are ecologically relevant and critical for tadpoles living in coastal brackish waters, improving their survival in coastal microhabitats with highly variable salinity levels.

Laser trapping-induced crystallization of L-phenylalanine through its high-concentration domain formation.

We present the laser trapping-induced crystallization of L-phenylalanine through high-concentration domain formation in H2O and D2O solutions which is achieved by focusing a continuous-wave (CW) near-infrared laser beam at the solution surface. Upon laser irradiation into the H2O solution, laser trapping of the liquid-like clusters increases the local concentration, accompanying laser heating, and a single plate-like crystal is eventually prepared at the focal spot. On the other hand, in the D2O solution, a lot of the monohydrate needle-like crystals are observed, not at the focal spot where the concentration is high enough to trigger crystal nucleation, but in the 0.5-1.5 mm range from the focal spot. The dynamics and mechanism of the amazing crystallization behaviour induced by laser trapping are discussed from the viewpoints of the concentration increase due to laser heating depending on solvent, the large high-concentration domain formation by laser trapping of liquid-like clusters, and the orientational disorder of molecules/clusters at the domain edge.

Carbon dioxide capture and functionalization by bis(N-heterocyclic carbene)-borylene complexes.

Derivatives of free monocoordinated borylenes have attracted considerable interest due to their ability to exhibit transition-metal-like reactivity, in particular small molecules capture. However, such complexes are rare as the formation is either endergonic, or the resulting adduct is a transient intermediate that is prone to reaction. Here, we present the synthesis of two bis(N-heterocyclic carbene)-borylene complexes capable of capturing and functionalizing carbon dioxide. The capture and subsequent functionalization of CO2 by the bis(NHC)-disilylamidoborylene 1 is demonstrated by the formation of the bis(NHC)-isocyanatoborylene-carbon dioxide complex 3. Reversible capture of CO2 is observed using the bis(NHC)-mesitylborylene 2, and the persistent bis(NHC)-mesitylborylene-carbon dioxide adduct 4 can be stabilized by hydrogen bonding with boric acid. The reactions of 4 with ammonia-borane and aniline demonstrate that the captured CO2 can be further functionalized.

Theoretical investigations of the reactivities of four-membered N-heterocyclic carbene analogues of the group 13 elements.

The potential energy surfaces for the chemical reactions of four-membered N-heterocyclic group 13 heavy carbeneoid species have been studied using density functional theory (Becke, 3-parameter, Lee-Yang-Parr (B3LYP)/Los Alamos National Laboratory 2-Double-Zeta (LANL2DZ)). Five four-membered group 13 heavy carbeneoid species, iPr2NC(NAr)2E:, where E » B, Al, Ga, In, and Tl, have been chosen as model reactants in this work. Also, three kinds of chemical reactions, CAH bond insertion, alkene cycloaddition, and dimerization, have been used to study the chemical reactivities of these group 13 fourmembered N-heterocyclic carbeneoid species. In principle, our present theoretical work predicts that the larger the ffNEN bond angle of the four-membered group 13 iPr2NC(NAr)2E: species, the smaller the singlet­triplet splitting, the lower the activation barrier, and, in turn, the more rapid its chemical reactions to various chemical species. Moreover, our theoretical investigations suggest that the relative carbenic reactivity decreases in the following order: B > Al > Ga > In > Tl. That is, the heavier the group 13 atom (E), the more stable its fourmembered carbeneoid toward chemical reactions is. As a result, our computations predict that the four-membered heavy group 13 iPr2NC(NAr)2E: species (E » Al, Ga, In, and Tl) should be both kinetically and thermodynamically stable, and can be readily synthesized and isolated at room temperature. Furthermore, the singlet­triplet energy splitting of the four-membered group 13 iPr2NC(NAr)2E: species, as described in the configuration mixing model attributed to the work of Pross and Shaik, can be used as a diagnostic tool to predict their reactivities. The results obtained allow a number of predictions to be made.

Irreversibility of a bad start: early exposure to osmotic stress limits growth and adaptive developmental plasticity.

Harsh environments experienced early in development have immediate effects and potentially long-lasting consequences throughout ontogeny. We examined how salinity fluctuations affected survival, growth and development of Fejervarya limnocharis tadpoles. Specifically, we tested whether initial salinity effects on growth and rates of development were reversible and whether they affected the tadpoles' ability to adaptively accelerate development in response to deteriorating conditions later in development. Tadpoles were initially assigned to either low or high salinity, and then some were switched between salinity levels upon reaching either Gosner stage 30 (early switch) or 38 (late switch). All tadpoles initially experiencing low salinity survived whereas those initially experiencing high salinity had poor survival, even if switched to low salinity. Growth and developmental rates of tadpoles initially assigned to high salinity did not increase after osmotic stress release. Initial low salinity conditions allowed tadpoles to attain a fast pace of development even if exposed to high salinity afterwards. Tadpoles experiencing high salinity only late in development metamorphosed faster and at a smaller size, indicating an adaptive acceleration of development to avoid osmotic stress. Nonetheless, early exposure to high salinity precluded adaptive acceleration of development, always causing delayed metamorphosis relative to those in initially low salinity. Our results thus show that stressful environments experienced early in development can critically impact life history traits, having long-lasting or irreversible effects, and restricting their ability to produce adaptive plastic responses.

Increasing salinity stress decreases the thermal tolerance of amphibian tadpoles in coastal areas of Taiwan.

Global warming is the main cause for the rise of both global temperatures and sea-level, both major variables threatening biodiversity. Rising temperatures threaten to breach the thermal limits of organisms while rising sea-level threatens the osmotic balance of coastal animals through habitat salinization. However, variations in thermal tolerance under different salinity stresses have not yet been thoroughly studied. In this study, we assessed the critical thermal maxima (CTmax) of amphibian tadpoles in different salinity conditions. We collected tadpoles of Duttaphrynus melanostictus, Fejervarya limnocharis and Microhyla fissipes from coastal areas and housed them in freshwater, low, and high salinity treatments for 7 days of acclimation. The CTmax, survival rate, and development rate of tadpoles in high salinity treatments were significantly lower than that of the two other treatments. Our results indicate that physiological performances and heat tolerances of tadpoles are negatively affected by salinization. Maximum entropy models showed that CTmax and sea-level rise are predicted to negatively affect the distribution of the three focal species. The present results suggest that global warming can lead to negative dual-impacts on coastal animals because of reduced thermal tolerances at elevated salinity. The impacts of global warming on anurans in coastal areas and other habitats impacted by salinization may be more severe than predicted and it is likely to cause similar dual-impacts on other ectotherms.

A computational study of the reactivities of four-membered heavy carbene systems.

The potential energy surfaces for the chemical reactions of four-membered N-heterocyclic group 14 heavy carbene species have been studied using density functional theory (B3LYP/LANL2DZ). Five four-membered group 14 heavy carbene species, (i-Pr)(2) NP(NR)(2) E:, in which E = C, Si, Ge, Sn, and Pb, were chosen as the model reactants in this work. Also, four kinds of chemical reactions, C-H bond insertion, water addition, alkene cycloaddition, and dimerization, have been used to study the chemical reactivities of these group 14 four-membered N-heterocyclic carbene species. Basically, our present theoretical work predicts that the larger the ∠NEN bond angle of the four-membered group 14 heavy carbene species, the smaller the singlet-triplet splitting, the lower the activation barrier, and, in turn, the more rapid, its chemical reactions to various chemical species. Moreover, our theoretical investigations suggest that the relative carbenic reactivity decreases in the order: C > Si > Ge > Sn > Pb. That is, the heavier the group 14 atom (E), the more stable is its four-membered carbene toward chemical reactions. As a result, our results predict that the four-membered group 14 heavy carbene species (E = Si, Ge, Sn, and Pb) should be more kinetically stable than the observed carbene species and, thus, can be also readily synthesized and isolated at room temperature. Furthermore, the singlet-triplet energy splitting of the four-membered group 14 carbene species, as described in the configuration mixing model attributed to the work of Pross and Shaik, can be used as a diagnostic tool to predict their reactivities. The results obtained allow a number of predictions to be made.

Effects of salinity on the survival, growth, development, and metamorphosis of Fejervarya limnocharis tadpoles living in brackish water.

We studied salinity tolerance and the effects of salinity on growth, development, and metamorphosis in Fejervarya limnocharis tadpoles living in brackish water. Specifically, we examined whether tadpoles exhibit adaptive plasticity in development when exposed to different salinities. Tadpoles collected on Green and Orchid Islands off Southeastern Taiwan were assigned to salinities of 0, 3, 5, 7, 9, 11, and 13 parts per thousand (ppt). The daily survival, weekly growth, and development of tadpoles were recorded until metamorphosis. More than 50% of tadpoles survived in 9 ppt for over a month, and a few individuals survived in 11 ppt for 20 days, suggesting that F. limnocharis tadpoles tolerate salinity better than the tadpoles of most species studied to date. Tadpoles at 9 ppt had lower survivorship, and retarded growth and development (from Gosner stage 26 to 35) compared to the other treatments. Tadpoles metamorphosed early at a smaller size as salinity increased, suggesting the existence of adaptive developmental plasticity in F. limnocharis in response to osmotic stress. Phenotypic plasticity in the age and size at metamorphosis in response to salinity may provide a means for tadpoles to adapt to the unpredictable salinity variation in coastal rock pools.

Salinity acclimation enhances salinity tolerance in tadpoles living in brackish water through increased Na⁺ , K⁺ -ATPase expression.

Amphibians are highly susceptible to osmotic stress but, nonetheless, some species can adapt locally to withstand moderately high levels of salinity. Maintaining the homeostasis of body fluids by efficient osmoregulation is thus critical for larval survival in saline environments. We studied the role of acclimation in increased physiological tolerance to elevated water salinity in the Indian rice frog (Fejervarya limnocharis) tadpoles exposed to brackish water. We quantified the effects of salinity acclimation on tadpole survival, osmolality, water content, and gill Na⁺ , K⁺ -ATPase (NKA) expression. Tadpoles did not survive over 12 hr if directly transferred to 11 ppt (parts per thousand) whereas tadpoles previously acclimated for 48 hr in 7 ppt survived at least 48 hr. We reared tadpoles in 3 ppt and then we transferred them to one of (a) 3 ppt, (b) 11 ppt, and (c) 7 ppt for 48 hr and then 11 ppt. In the first 6 hr after transfer to 11 ppt, tadpole osmolality sharply increased and tadpole water content decreased. Tadpoles pre-acclimated for 48 hr in 7 ppt were able to maintain lower and more stable osmolality within the first 3 hr after transfer. These tadpoles initially lost water content, but over the next 6 hr gradually regained water and stabilized. In addition, they had a higher relative abundance of NKA proteins than tadpoles in other treatments. Pre-acclimation to 7 ppt for 48 hr was hence sufficient to activate NKA expression, resulting in increased survivorship and reduced dehydration upon later transfer to 11 ppt. J

Reactivity for boryl(phosphino)carbenyl carbene analogues with group 14 elements (C, Si, Ge, Sb, and Pb) as a heteroatom: a theoretical study.

The potential energy surfaces for the chemical reactions of group 14 carbenes have been studied using density functional theory (B3LYP/LANL2DZ). Five boryl(phosphino)-based carbene (B-Ë-P) species, where Ë = C, Si, Ge, Sn, and Pb, have been chosen as model reactants in this work. Also, four kinds of chemical reactions; intramolecular 1,2-migration, water insertion, alkene cycloaddition, and intermolecular dimerization, have been used to study the chemical reactivities of these group 14 carbenes. The present theoretical investigations suggest that the relative carbenic reactivity decreases in the order C > Si > Ge > Sn > Pb. That is, the heavier the group 14 atom (E), the more stable is the boryl(phosphino)-based B-Ë-P species towards chemical reactions. Our theoretical findings thus demonstrate that all boryl(phosphino)-based carbenes are isolable at room temperature because they are quite inert to chemical reactions, except that they are also moisture-sensitive molecules. Furthermore, the singlet-triplet energy splitting of the B-Ë-P, as described in the configuration mixing model attributed to the work of Pross and Shaik, can serve as a diagnostic tool for a better understanding and predicting of their chemical reactivities, kinetically and thermodynamically. The results obtained allow a number of predictions to be made.