Heterobimetallic Trihydrido Complex of Ruthenium and Rhodium Supported by Cyclopentadienyl Groups with Different Steric Demands

The reactivity of heterobimetallic trihydrido complexes of Ru and Rh supported by two kinds of cyclopentadienyl groups that provide steric differentiation in the dinuclear reaction field, [CpsRu(μ-H)3RhCps] (3b: CpsRuCp‡Ru, CpsRhCp*Rh, 3c: CpsRuCp*Ru, CpsRhCp‡Rh; Cp‡1,2,4-tBu3C5H2, Cp*C5Me5), was examined to elucidate the role of each metal center. Since the bulky Cp‡ group on the Ru center in 3b retarded the uptake of diphenylacetylene, complex 3b reacted with diphenylacetylene at 60 °C to yield benzorhodacyclopentadiene complex 7b via the cyclometalation at the Rh center. In contrast, complex 3c, which contains a less congested Ru center, reacted with diphenylacetylene smoothly at 25 °C and afforded μ-alkenyl and μ-alkyne complexes, 5c and 6c. The rhodacyclopentadiene complex 7c was also obtained upon thermolysis of 6c but required heating at 180 °C. The reactivity toward acetylene did not differ from each other due to its high reactivity and μ-s-cis-η2:η2-butadiene-μ-vinyl complexes, 10b and 10c, were obtained. Although no intermediate was observed in the reaction, DFT calculations for a model compound supported by unsubstituted cyclopentadienyls suggested the exclusive uptake of acetylene at the Ru center. Complex 3b reacted with benzene at 25 °C under photo-irradiating conditions to yield μ-phenyl complex 11b in 52% yield, although 3c decomposed under the same conditions. The reason why a μ-phenyl complex was not formed in the photoreaction of 3c is that the Cp‡ group on the Rh center suppressed the intramolecular migration of the phenyl group from the Ru to the Rh center. Instead, the decomposition induced by the coordination of additional benzene molecules to the Ru center was not suppressed. These results demonstrated that the Ru center acts as an initial binding site, although it is difficult to determine directly from the structure of the product

Heterobimetallic Trihydrido Complex of Ruthenium and Rhodium Supported by Cyclopentadienyl Groups with Different Steric Demands

The reactivity of heterobimetallic trihydrido complexes of Ru and Rh supported by two kinds of cyclopentadienyl groups that provide steric differentiation in the dinuclear reaction field, [CpsRu(μ-H)3RhCps] (3b: CpsRuCp‡Ru, CpsRhCp*Rh, 3c: CpsRuCp*Ru, CpsRhCp‡Rh; Cp‡1,2,4-tBu3C5H2, Cp*C5Me5), was examined to elucidate the role of each metal center. Since the bulky Cp‡ group on the Ru center in 3b retarded the uptake of diphenylacetylene, complex 3b reacted with diphenylacetylene at 60 °C to yield benzorhodacyclopentadiene complex 7b via the cyclometalation at the Rh center. In contrast, complex 3c, which contains a less congested Ru center, reacted with diphenylacetylene smoothly at 25 °C and afforded μ-alkenyl and μ-alkyne complexes, 5c and 6c. The rhodacyclopentadiene complex 7c was also obtained upon thermolysis of 6c but required heating at 180 °C. The reactivity toward acetylene did not differ from each other due to its high reactivity and μ-s-cis-η2:η2-butadiene-μ-vinyl complexes, 10b and 10c, were obtained. Although no intermediate was observed in the reaction, DFT calculations for a model compound supported by unsubstituted cyclopentadienyls suggested the exclusive uptake of acetylene at the Ru center. Complex 3b reacted with benzene at 25 °C under photo-irradiating conditions to yield μ-phenyl complex 11b in 52% yield, although 3c decomposed under the same conditions. The reason why a μ-phenyl complex was not formed in the photoreaction of 3c is that the Cp‡ group on the Rh center suppressed the intramolecular migration of the phenyl group from the Ru to the Rh center. Instead, the decomposition induced by the coordination of additional benzene molecules to the Ru center was not suppressed. These results demonstrated that the Ru center acts as an initial binding site, although it is difficult to determine directly from the structure of the product

Heterobimetallic Trihydrido Complex of Ruthenium and Rhodium Supported by Cyclopentadienyl Groups with Different Steric Demands

The reactivity of heterobimetallic trihydrido complexes of Ru and Rh supported by two kinds of cyclopentadienyl groups that provide steric differentiation in the dinuclear reaction field, [CpsRu(μ-H)3RhCps] (3b: CpsRuCp‡Ru, CpsRhCp*Rh, 3c: CpsRuCp*Ru, CpsRhCp‡Rh; Cp‡1,2,4-tBu3C5H2, Cp*C5Me5), was examined to elucidate the role of each metal center. Since the bulky Cp‡ group on the Ru center in 3b retarded the uptake of diphenylacetylene, complex 3b reacted with diphenylacetylene at 60 °C to yield benzorhodacyclopentadiene complex 7b via the cyclometalation at the Rh center. In contrast, complex 3c, which contains a less congested Ru center, reacted with diphenylacetylene smoothly at 25 °C and afforded μ-alkenyl and μ-alkyne complexes, 5c and 6c. The rhodacyclopentadiene complex 7c was also obtained upon thermolysis of 6c but required heating at 180 °C. The reactivity toward acetylene did not differ from each other due to its high reactivity and μ-s-cis-η2:η2-butadiene-μ-vinyl complexes, 10b and 10c, were obtained. Although no intermediate was observed in the reaction, DFT calculations for a model compound supported by unsubstituted cyclopentadienyls suggested the exclusive uptake of acetylene at the Ru center. Complex 3b reacted with benzene at 25 °C under photo-irradiating conditions to yield μ-phenyl complex 11b in 52% yield, although 3c decomposed under the same conditions. The reason why a μ-phenyl complex was not formed in the photoreaction of 3c is that the Cp‡ group on the Rh center suppressed the intramolecular migration of the phenyl group from the Ru to the Rh center. Instead, the decomposition induced by the coordination of additional benzene molecules to the Ru center was not suppressed. These results demonstrated that the Ru center acts as an initial binding site, although it is difficult to determine directly from the structure of the product

Heterobimetallic Trihydrido Complex of Ruthenium and Rhodium Supported by Cyclopentadienyl Groups with Different Steric Demands

The reactivity of heterobimetallic trihydrido complexes of Ru and Rh supported by two kinds of cyclopentadienyl groups that provide steric differentiation in the dinuclear reaction field, [CpsRu(μ-H)3RhCps] (3b: CpsRuCp‡Ru, CpsRhCp*Rh, 3c: CpsRuCp*Ru, CpsRhCp‡Rh; Cp‡1,2,4-tBu3C5H2, Cp*C5Me5), was examined to elucidate the role of each metal center. Since the bulky Cp‡ group on the Ru center in 3b retarded the uptake of diphenylacetylene, complex 3b reacted with diphenylacetylene at 60 °C to yield benzorhodacyclopentadiene complex 7b via the cyclometalation at the Rh center. In contrast, complex 3c, which contains a less congested Ru center, reacted with diphenylacetylene smoothly at 25 °C and afforded μ-alkenyl and μ-alkyne complexes, 5c and 6c. The rhodacyclopentadiene complex 7c was also obtained upon thermolysis of 6c but required heating at 180 °C. The reactivity toward acetylene did not differ from each other due to its high reactivity and μ-s-cis-η2:η2-butadiene-μ-vinyl complexes, 10b and 10c, were obtained. Although no intermediate was observed in the reaction, DFT calculations for a model compound supported by unsubstituted cyclopentadienyls suggested the exclusive uptake of acetylene at the Ru center. Complex 3b reacted with benzene at 25 °C under photo-irradiating conditions to yield μ-phenyl complex 11b in 52% yield, although 3c decomposed under the same conditions. The reason why a μ-phenyl complex was not formed in the photoreaction of 3c is that the Cp‡ group on the Rh center suppressed the intramolecular migration of the phenyl group from the Ru to the Rh center. Instead, the decomposition induced by the coordination of additional benzene molecules to the Ru center was not suppressed. These results demonstrated that the Ru center acts as an initial binding site, although it is difficult to determine directly from the structure of the product

Movie 03 from Plant-inspired pipettes

Successful grabbing of olive oil during a fast withdrawal

Movie 01 from Plant-inspired pipettes

Successful grabbing of water during a fast withdrawa

Movie 4 from Plant-inspired pipettes

Successful grabbing of olive oil during a slow withdrawa

Movie 02 from Plant-inspired pipettes

Successful grabbing of water during a slow withdrawa

Endometrial factors similarly induced by IFNT2 and IFNTc1 through transcription factor FOXS1

<div><p>In ruminants, Interferon tau (IFNT) is the pregnancy recognition protein produced by the mononuclear trophectoderm of the conceptus, and is secreted into the uterine lumen during the peri-attachment period. In our previous study, the high-throughput RNA sequencing (RNA-seq) data obtained from bovine conceptuses during the peri-attachment period identified two <i>IFNT</i> mRNAs, <i>IFNT2</i> and <i>IFNTc1</i>. However, how each of these IFNT variants regulates endometrial gene expression has not been characterized. Using RNA-seq analysis, we evaluated how IFNT2 and IFNTc1 affected transcript expression in primary bovine endometrial epithelial cells (EECs). IFNT treatment induced 348 differentially expressed genes (DEGs); however, there are few DEGs in IFNT2 or IFNTc1 treated EECs, indicating that IFNT2-induced DEGs were similar to those induced by IFNTc1 treatment. In in silico analysis, we identified four IFNT2- and IFNTc1-induced pathways: 1) type II interferon signaling, 2) proteasome degradation, 3) type III interferon signaling, and 4) DNA damage response. We further demonstrated that IFNT2 and IFNTc1 up-regulated several transcription factors, among which forkhead box S1 (<i>FOXS1</i>) was identified as the most highly expressed gene. Furthermore, the knockdown of <i>FOXS1</i> in IFNT2- or IFNTc1-treated EECs similarly down-regulated 9 genes including <i>IRF3</i> and <i>IRF9</i>, and up-regulated 9 genes including <i>STAT1</i>, <i>STAT2</i>, and <i>IRF8</i>. These represent the first demonstration that effects of each IFNT on EECs were studied, and suggest that endometrial response as well as signaling mechanisms were similar between two IFNT variants existed in utero.</p></div

Identification of gene expression induced by IFNTs in EECs.

<p>EECs were incubated without (Ctrl) or with IFNT2 or IFNTc1 (2 x 10⁵ cells/5000 IU/well) for 24 h. RNA was extracted from the EECs and subjected to real-time PCR analysis to determine gene expression related to type II interferon, proteasome degradation, type III interferon, and DNA damage response signaling in Ctrl, IFNT2-, or IFNTc1-treated EECs (n = 3 each group). <i>GAPDH</i> mRNA was used as an internal control for RNA integrity. ^aP < 0.01, ^bP<0.05 vs. Ctrl. Value represent the mean ± SEM from three independent experiments in each treatment.</p