Conversion of a Hydrido–Butenylcarbyne Complex to η²‑Allene-Coordinated Complexes and Metallabenzenes

Treatment of OsCl₂(PPh₃)₃ with HCCCH­(OH)­Et produces the cyclic complex Os­(PPh₃)₂Cl₂(CHC­(PPh₃)­CH­(OH)­CH₂CH₃) (<b>1</b>), which can undergo dehydration to give the hydrido–alkenylvinylidene complex Os­(PPh₃)₂HCl₂(CC­(PPh₃)­CHCHCH₃) (<b>2</b>). Reaction of <b>2</b> with HBF₄ generates the hydrido–butenylcarbyne complex [OsHCl₂(CC­(PPh₃)CH­(Et))­(PPh₃)₂]­BF₄ (<b>3</b>). The complex <b>3</b> evolves into the unstable metallabenzene [(PPh₃)₂(RCN)­ClOs­(CHC­(PPh₃)­CHCHCH)]­BF₄ (<b>4</b>; RCN = benzonitrile, 2-cyanobenzaldehyde, 3-methoxyacrylonitrile, 2-cyanoacetamide) via triple hydrogen eliminations in the presence of excess nitriles in refluxing CHCl₃ in an air atmosphere. The ligand substitution reaction of <b>4</b> with excess CO affords the stable metallabenzene product [(PPh₃)₂(CO)­ClOs­(CHC­(PPh₃)­CHCHCH)]­BF₄ (<b>5</b>). The key intermediates, η²-allene-coordinated osmium complexes [(PPh₃)₂(RCN)­ClOs­(CHC­(PPh₃)­CHCCH₂)]­BF₄ (<b>6</b>; RCN = benzonitrile, 2-cyanobenzaldehyde, 3-methoxyacrylonitrile, 2-cyanoacetamide) can be captured by performing the conversion at room temperature. Remarkably, in the absence of nitriles, reaction of <b>3</b> with excess CO only generates the vinylethenyl complex [(PPh₃)₂(CO)₂ClOs­(CHC­(PPh₃)­CHCHCH₃)]­BF₄ (<b>7</b>). The complexes <b>1</b>–<b>3</b>, <b>5</b>, <b>6a</b>, and <b>7</b> have been structurally characterized by single-crystal X-ray diffraction. Detailed mechanisms of the conversions have been investigated with the aid of density functional theory (DFT) calculations. DFT calculations suggest that the high stablility of the carbonyl coordinated complexes in the conversion inhibits the further transformation to metallabenzene product. However, the transformation is both kinetically and thermodynamically favorable in the presence of the relatively weaker nitrile ligand, which is consistent with the experimental conversion of <b>3</b> to <b>5</b> via unstable metallabenzenes <b>4</b> observed for in situ NMR experiments

Conversion of a Hydrido–Butenylcarbyne Complex to η²‑Allene-Coordinated Complexes and Metallabenzenes

Treatment of OsCl₂(PPh₃)₃ with HCCCH­(OH)­Et produces the cyclic complex Os­(PPh₃)₂Cl₂(CHC­(PPh₃)­CH­(OH)­CH₂CH₃) (<b>1</b>), which can undergo dehydration to give the hydrido–alkenylvinylidene complex Os­(PPh₃)₂HCl₂(CC­(PPh₃)­CHCHCH₃) (<b>2</b>). Reaction of <b>2</b> with HBF₄ generates the hydrido–butenylcarbyne complex [OsHCl₂(CC­(PPh₃)CH­(Et))­(PPh₃)₂]­BF₄ (<b>3</b>). The complex <b>3</b> evolves into the unstable metallabenzene [(PPh₃)₂(RCN)­ClOs­(CHC­(PPh₃)­CHCHCH)]­BF₄ (<b>4</b>; RCN = benzonitrile, 2-cyanobenzaldehyde, 3-methoxyacrylonitrile, 2-cyanoacetamide) via triple hydrogen eliminations in the presence of excess nitriles in refluxing CHCl₃ in an air atmosphere. The ligand substitution reaction of <b>4</b> with excess CO affords the stable metallabenzene product [(PPh₃)₂(CO)­ClOs­(CHC­(PPh₃)­CHCHCH)]­BF₄ (<b>5</b>). The key intermediates, η²-allene-coordinated osmium complexes [(PPh₃)₂(RCN)­ClOs­(CHC­(PPh₃)­CHCCH₂)]­BF₄ (<b>6</b>; RCN = benzonitrile, 2-cyanobenzaldehyde, 3-methoxyacrylonitrile, 2-cyanoacetamide) can be captured by performing the conversion at room temperature. Remarkably, in the absence of nitriles, reaction of <b>3</b> with excess CO only generates the vinylethenyl complex [(PPh₃)₂(CO)₂ClOs­(CHC­(PPh₃)­CHCHCH₃)]­BF₄ (<b>7</b>). The complexes <b>1</b>–<b>3</b>, <b>5</b>, <b>6a</b>, and <b>7</b> have been structurally characterized by single-crystal X-ray diffraction. Detailed mechanisms of the conversions have been investigated with the aid of density functional theory (DFT) calculations. DFT calculations suggest that the high stablility of the carbonyl coordinated complexes in the conversion inhibits the further transformation to metallabenzene product. However, the transformation is both kinetically and thermodynamically favorable in the presence of the relatively weaker nitrile ligand, which is consistent with the experimental conversion of <b>3</b> to <b>5</b> via unstable metallabenzenes <b>4</b> observed for in situ NMR experiments

Mechanistic Study of Indolizine Heterocycle Formation by Ruthenium(II)-Assisted Three-Component Cross-Coupling<b>/</b>Cyclization

In the presence of the acid HBF₄, 3-alkenyl-2-phosphonium indolizines <b>3a</b>–<b>c</b> can be produced respectively by adding PhCCCOCH₃ (<b>2a</b>), CH₃OCOCCCOOCH₃ (<b>2b</b>), and CH₃CH₂CCCOCH₃ (<b>2c</b>) to a mixture of ruthenium complex RuCl₂(PPh₃)₃ and the propargyl alcohol (2-Py)­CH­(OH)­CCH (<b>1</b>). We carefully investigated the mechanism of this reaction by means of structurally characterizing two key intermediates, ruthenium vinyl (<b>4</b>) and ruthenium carbene (<b>5</b>), and by deuterium-labeling experiments. A plausible mechanism is proposed, which involves addition of a proton to an alkyne carbon and the insertion of an alkyne into the Cα bond of an alkenylcarbene group, followed by an α<i>-</i>H elimination and reductive elimination

DataSheet_1_Comprehensive resistance evaluation of 15 blueberry cultivars under high soil pH stress based on growth phenotype and physiological traits.docx

High soil pH is one of the main abiotic factors that negatively affects blueberry growth and cultivation. However, no comprehensive evaluation of the high soil pH tolerance of different blueberry cultivars has been conducted. Herein, 16 phenotypic and physiological indices of 15 blueberry cultivars were measured through pot experiments, and the high-pH soil tolerance coefficient (HSTC) was calculated based on these indices to comprehensively evaluate the high-soil-pH tolerance of plants. The results demonstrated that high soil pH stress inhibited blueberry 77.growth, and MDA, soluble sugar (SS), and soluble protein (SP) levels increased in leaves. Moreover, in all cultivars, CAT activity in the antioxidant system was enhanced, whereas SOD activity was reduced, and the relative expression levels of the antioxidant enzyme genes SOD and CAT showed similar changes. In addition, the leaf chlorophyll relative content (SPAD), net photosynthetic rate (Pn), transpiration rate (E), and stomatal conductance (Gs) decreased, while changes in the intercellular CO2 concentration (Ci) were noted in different cultivars. Finally, according to the comprehensive evaluation value D obtained from the combination of principal component analysis (PCA) and membership function (MF), the 15 blueberry cultivars can be divided into 4 categories: high soil pH-tolerant type [‘Briteblue’ (highest D value 0.815)], intermediate tolerance type (‘Zhaixuan 9’, ‘Zhaixuan 7’, ‘Emerald’, ‘Primadonna’, ‘Powderblue’ and ‘Chandler’), low high soil pH-tolerant type (‘Brightwell’, ‘Gardenblue’, ‘Plolific’ and ‘Sharpblue’) and high soil pH-sensitive type [‘Legacy’, ‘Bluegold’, ‘Baldwin’ and ‘Anna’ (lowest D value 0.166)]. Stepwise linear regression analysis revealed that plant height, SS, E, leaf length, Ci, SOD, and SPAD could be used to predict and evaluate the high soil pH tolerance of blueberry cultivars.</p

Conversion of a Hydrido–Butenylcarbyne Complex to η²‑Allene-Coordinated Complexes and Metallabenzenes

Treatment of OsCl₂(PPh₃)₃ with HCCCH­(OH)­Et produces the cyclic complex Os­(PPh₃)₂Cl₂(CHC­(PPh₃)­CH­(OH)­CH₂CH₃) (<b>1</b>), which can undergo dehydration to give the hydrido–alkenylvinylidene complex Os­(PPh₃)₂HCl₂(CC­(PPh₃)­CHCHCH₃) (<b>2</b>). Reaction of <b>2</b> with HBF₄ generates the hydrido–butenylcarbyne complex [OsHCl₂(CC­(PPh₃)CH­(Et))­(PPh₃)₂]­BF₄ (<b>3</b>). The complex <b>3</b> evolves into the unstable metallabenzene [(PPh₃)₂(RCN)­ClOs­(CHC­(PPh₃)­CHCHCH)]­BF₄ (<b>4</b>; RCN = benzonitrile, 2-cyanobenzaldehyde, 3-methoxyacrylonitrile, 2-cyanoacetamide) via triple hydrogen eliminations in the presence of excess nitriles in refluxing CHCl₃ in an air atmosphere. The ligand substitution reaction of <b>4</b> with excess CO affords the stable metallabenzene product [(PPh₃)₂(CO)­ClOs­(CHC­(PPh₃)­CHCHCH)]­BF₄ (<b>5</b>). The key intermediates, η²-allene-coordinated osmium complexes [(PPh₃)₂(RCN)­ClOs­(CHC­(PPh₃)­CHCCH₂)]­BF₄ (<b>6</b>; RCN = benzonitrile, 2-cyanobenzaldehyde, 3-methoxyacrylonitrile, 2-cyanoacetamide) can be captured by performing the conversion at room temperature. Remarkably, in the absence of nitriles, reaction of <b>3</b> with excess CO only generates the vinylethenyl complex [(PPh₃)₂(CO)₂ClOs­(CHC­(PPh₃)­CHCHCH₃)]­BF₄ (<b>7</b>). The complexes <b>1</b>–<b>3</b>, <b>5</b>, <b>6a</b>, and <b>7</b> have been structurally characterized by single-crystal X-ray diffraction. Detailed mechanisms of the conversions have been investigated with the aid of density functional theory (DFT) calculations. DFT calculations suggest that the high stablility of the carbonyl coordinated complexes in the conversion inhibits the further transformation to metallabenzene product. However, the transformation is both kinetically and thermodynamically favorable in the presence of the relatively weaker nitrile ligand, which is consistent with the experimental conversion of <b>3</b> to <b>5</b> via unstable metallabenzenes <b>4</b> observed for in situ NMR experiments

Conversion of a Hydrido–Butenylcarbyne Complex to η²‑Allene-Coordinated Complexes and Metallabenzenes

Treatment of OsCl₂(PPh₃)₃ with HCCCH­(OH)­Et produces the cyclic complex Os­(PPh₃)₂Cl₂(CHC­(PPh₃)­CH­(OH)­CH₂CH₃) (<b>1</b>), which can undergo dehydration to give the hydrido–alkenylvinylidene complex Os­(PPh₃)₂HCl₂(CC­(PPh₃)­CHCHCH₃) (<b>2</b>). Reaction of <b>2</b> with HBF₄ generates the hydrido–butenylcarbyne complex [OsHCl₂(CC­(PPh₃)CH­(Et))­(PPh₃)₂]­BF₄ (<b>3</b>). The complex <b>3</b> evolves into the unstable metallabenzene [(PPh₃)₂(RCN)­ClOs­(CHC­(PPh₃)­CHCHCH)]­BF₄ (<b>4</b>; RCN = benzonitrile, 2-cyanobenzaldehyde, 3-methoxyacrylonitrile, 2-cyanoacetamide) via triple hydrogen eliminations in the presence of excess nitriles in refluxing CHCl₃ in an air atmosphere. The ligand substitution reaction of <b>4</b> with excess CO affords the stable metallabenzene product [(PPh₃)₂(CO)­ClOs­(CHC­(PPh₃)­CHCHCH)]­BF₄ (<b>5</b>). The key intermediates, η²-allene-coordinated osmium complexes [(PPh₃)₂(RCN)­ClOs­(CHC­(PPh₃)­CHCCH₂)]­BF₄ (<b>6</b>; RCN = benzonitrile, 2-cyanobenzaldehyde, 3-methoxyacrylonitrile, 2-cyanoacetamide) can be captured by performing the conversion at room temperature. Remarkably, in the absence of nitriles, reaction of <b>3</b> with excess CO only generates the vinylethenyl complex [(PPh₃)₂(CO)₂ClOs­(CHC­(PPh₃)­CHCHCH₃)]­BF₄ (<b>7</b>). The complexes <b>1</b>–<b>3</b>, <b>5</b>, <b>6a</b>, and <b>7</b> have been structurally characterized by single-crystal X-ray diffraction. Detailed mechanisms of the conversions have been investigated with the aid of density functional theory (DFT) calculations. DFT calculations suggest that the high stablility of the carbonyl coordinated complexes in the conversion inhibits the further transformation to metallabenzene product. However, the transformation is both kinetically and thermodynamically favorable in the presence of the relatively weaker nitrile ligand, which is consistent with the experimental conversion of <b>3</b> to <b>5</b> via unstable metallabenzenes <b>4</b> observed for in situ NMR experiments

Conversion of a Hydrido–Butenylcarbyne Complex to η²‑Allene-Coordinated Complexes and Metallabenzenes

Treatment of OsCl₂(PPh₃)₃ with HCCCH­(OH)­Et produces the cyclic complex Os­(PPh₃)₂Cl₂(CHC­(PPh₃)­CH­(OH)­CH₂CH₃) (<b>1</b>), which can undergo dehydration to give the hydrido–alkenylvinylidene complex Os­(PPh₃)₂HCl₂(CC­(PPh₃)­CHCHCH₃) (<b>2</b>). Reaction of <b>2</b> with HBF₄ generates the hydrido–butenylcarbyne complex [OsHCl₂(CC­(PPh₃)CH­(Et))­(PPh₃)₂]­BF₄ (<b>3</b>). The complex <b>3</b> evolves into the unstable metallabenzene [(PPh₃)₂(RCN)­ClOs­(CHC­(PPh₃)­CHCHCH)]­BF₄ (<b>4</b>; RCN = benzonitrile, 2-cyanobenzaldehyde, 3-methoxyacrylonitrile, 2-cyanoacetamide) via triple hydrogen eliminations in the presence of excess nitriles in refluxing CHCl₃ in an air atmosphere. The ligand substitution reaction of <b>4</b> with excess CO affords the stable metallabenzene product [(PPh₃)₂(CO)­ClOs­(CHC­(PPh₃)­CHCHCH)]­BF₄ (<b>5</b>). The key intermediates, η²-allene-coordinated osmium complexes [(PPh₃)₂(RCN)­ClOs­(CHC­(PPh₃)­CHCCH₂)]­BF₄ (<b>6</b>; RCN = benzonitrile, 2-cyanobenzaldehyde, 3-methoxyacrylonitrile, 2-cyanoacetamide) can be captured by performing the conversion at room temperature. Remarkably, in the absence of nitriles, reaction of <b>3</b> with excess CO only generates the vinylethenyl complex [(PPh₃)₂(CO)₂ClOs­(CHC­(PPh₃)­CHCHCH₃)]­BF₄ (<b>7</b>). The complexes <b>1</b>–<b>3</b>, <b>5</b>, <b>6a</b>, and <b>7</b> have been structurally characterized by single-crystal X-ray diffraction. Detailed mechanisms of the conversions have been investigated with the aid of density functional theory (DFT) calculations. DFT calculations suggest that the high stablility of the carbonyl coordinated complexes in the conversion inhibits the further transformation to metallabenzene product. However, the transformation is both kinetically and thermodynamically favorable in the presence of the relatively weaker nitrile ligand, which is consistent with the experimental conversion of <b>3</b> to <b>5</b> via unstable metallabenzenes <b>4</b> observed for in situ NMR experiments

Conversion of a Hydrido–Butenylcarbyne Complex to η²‑Allene-Coordinated Complexes and Metallabenzenes

Treatment of OsCl₂(PPh₃)₃ with HCCCH­(OH)­Et produces the cyclic complex Os­(PPh₃)₂Cl₂(CHC­(PPh₃)­CH­(OH)­CH₂CH₃) (<b>1</b>), which can undergo dehydration to give the hydrido–alkenylvinylidene complex Os­(PPh₃)₂HCl₂(CC­(PPh₃)­CHCHCH₃) (<b>2</b>). Reaction of <b>2</b> with HBF₄ generates the hydrido–butenylcarbyne complex [OsHCl₂(CC­(PPh₃)CH­(Et))­(PPh₃)₂]­BF₄ (<b>3</b>). The complex <b>3</b> evolves into the unstable metallabenzene [(PPh₃)₂(RCN)­ClOs­(CHC­(PPh₃)­CHCHCH)]­BF₄ (<b>4</b>; RCN = benzonitrile, 2-cyanobenzaldehyde, 3-methoxyacrylonitrile, 2-cyanoacetamide) via triple hydrogen eliminations in the presence of excess nitriles in refluxing CHCl₃ in an air atmosphere. The ligand substitution reaction of <b>4</b> with excess CO affords the stable metallabenzene product [(PPh₃)₂(CO)­ClOs­(CHC­(PPh₃)­CHCHCH)]­BF₄ (<b>5</b>). The key intermediates, η²-allene-coordinated osmium complexes [(PPh₃)₂(RCN)­ClOs­(CHC­(PPh₃)­CHCCH₂)]­BF₄ (<b>6</b>; RCN = benzonitrile, 2-cyanobenzaldehyde, 3-methoxyacrylonitrile, 2-cyanoacetamide) can be captured by performing the conversion at room temperature. Remarkably, in the absence of nitriles, reaction of <b>3</b> with excess CO only generates the vinylethenyl complex [(PPh₃)₂(CO)₂ClOs­(CHC­(PPh₃)­CHCHCH₃)]­BF₄ (<b>7</b>). The complexes <b>1</b>–<b>3</b>, <b>5</b>, <b>6a</b>, and <b>7</b> have been structurally characterized by single-crystal X-ray diffraction. Detailed mechanisms of the conversions have been investigated with the aid of density functional theory (DFT) calculations. DFT calculations suggest that the high stablility of the carbonyl coordinated complexes in the conversion inhibits the further transformation to metallabenzene product. However, the transformation is both kinetically and thermodynamically favorable in the presence of the relatively weaker nitrile ligand, which is consistent with the experimental conversion of <b>3</b> to <b>5</b> via unstable metallabenzenes <b>4</b> observed for in situ NMR experiments

Synthesis of One-Handed Helical Block Copoly(substituted acetylene)s Consisting of Dynamic <i>cis-transoidal</i> and Static <i>cis-cisoidal</i> Block: Chiral Teleinduction in Helix-Sense-Selective Polymerization Using a Chiral Living Polymer as an Initiator

By using a living one-handed helical <i>cis-transoidal</i> poly­(chiral substituted phenylacetylene) as a polymer initiator (poly­(<b>1</b>_n)), helix-sense-selective polymerization (<b>HSSP</b>) of an achiral phenylacetylene <b>2</b> having two hydroxy groups successfully afforded a diblock copoly­(phenylacetylene) (copoly­(<b>1</b>_n/<b>2</b>_m)) consisting of a dynamic one-handed helical <i>cis-transoidal</i> block and a static one-handed helical <i>cis-cisoidal</i> block. The formation of the diblock structure was confirmed by consumption of the chiral initiator, appearance of characteristic CD indicating the one-handed helical <i>cis-cisoidal</i> block, and occurrence of the selective photocylic aromatization reaction in the <i>cis-cisoidal</i> block. Therefore, <b>HSSP</b> has been achieved by using the chiral alkenyl groups in the initiator as a chiral source for the first time. In addition, since the <b>HSSP</b> was achieved in spite of the long distance between the chiral initiation site and the propagating site, chiral teleinduction through the rigid and static one-handed helical <i>cis</i>-cisoidal block based on domino effects was confirmed

Exploring the Segregating and Mineralization-Inducing Capacities of Cationic Hydrophilic Polymers for Preparation of Robust, Multifunctional Mesoporous Hybrid Microcapsules

A facile approach to preparing mesoporous hybrid microcapsules is developed by exploring the segregating and mineralization-inducing capacities of cationic hydrophilic polymer. The preparation process contains four steps: segregation of cationic hydrophilic polymer during template formation, cross-linking of the segregated polymer, biomimetic mineralization within cross-linked polymer network, and removal of template to simultaneously generate capsule lumen and mesopores on the capsule wall. Poly­(allylamine hydrochloride) (PAH) is chosen as the model polymer, its hydrophilicity renders the segregating capacity and spontaneous enrichment in the near-surface region of CaCO₃ microspheres; its biopolyamine-mimic structure renders the mineralization-inducing capacity to produce titania from the water-soluble titanium­(IV) precursor. Meanwhile, CaCO₃ microspheres serve the dual templating functions in the formation of hollow lumen and mesoporous wall. The thickness of capsule wall can be controlled by changing the polymer segregating and cross-linking conditions, while the pore size on the capsule wall can be tuned by changing the template synthesizing conditions. The robust hybrid microcapsules exhibit desirable efficiency in enzymatic catalysis, wastewater treatment and drug delivery. This approach may open facile, generic, and efficient pathway to designing and preparing a variety of hybrid microcapsules with high and tunable permeability, good stability and multiple functionalities for a broad range of applications