Dipalladium Complexes with Bridging Monoalkyl or Monophenyl Silyl Ligands in the Solid State and in Solution

HexSiH₃, PhSiH₃, and PhSiClH₂ reacted with [Pd­(PCy₃)₂] to yield dipalladium complexes with bridging silyl ligands: [{Pd­(PCy₃)}₂(μ-HSiXR)₂] (<b>1</b>, R = Hex, X = H; <b>2</b>, R = Ph, X = H; <b>3</b>, R = Ph, X = Cl). The X-ray crystallographic results displayed a typical bis­(silyl)-bridged dinuclear structure with an anti conformation of the substituents on the Si atom in the solid state. Temperature-dependent NMR spectroscopic analyses of <b>1</b> and <b>2</b> revealed a dynamic <i>syn</i>–<i>anti</i> isomerization of the complex via exchange of the bridging and nonbridging Si–H hydrogens in solution. Complex <b>3</b> with bridging chloro­(phenyl)­silyl ligands did not show such a dynamic behavior

Nickel-Catalyzed Cyclopolymerization of Hexyl- and Phenylsilanes

[Ni­(dmpe)₂] (dmpe = 1,2-bis­(dimethylphosphino)­ethane) catalyzed the dehydrogenative polymerization of hexylsilane in toluene at room temperature to produce a mixture of acyclic and cyclic poly­(hexylsilanes). A simlar reaction at 70 °C resulted in selective cyclopolymerization of hexylsilane to yield a cyclic polymer with an average molecular weight of <i>M</i>_n = 1450 (<i>M</i>_w/<i>M</i>_n = 1.01, GPC polystyrene standard). The ¹H NMR, ²⁹Si­{¹H} DEPT NMR, and IR spectroscopic data indicated the presence or absence of the −SiH₂R end groups of the polymer and its acyclic or cyclic structure. Addition of hexylsilane to the solution of the poly­(hexylsilanes) containing the acyclic polymer (<i>M</i>_n = 1330) and heating the mixture in the presence of 5 mol % of [Ni­(dmpe)₂] catalyst formed a polymer composed of the cyclic molecules without a change in the average molecular weight. The polymerization of phenylsilane catalyzed by [Ni­(dmpe)₂] also yielded the cyclic poly­(phenylsilane). The reaction using a mixture of [Ni­(cod)₂] (cod = 1,5-cyclooctadiene) and PMe₃ as the catalyst produced acyclic and/or cyclic poly­(phenylsilanes) depending on the conditions. 9,9-Dihydrosilafluorene reacted with [PdMe₂(dmpe)] to afford a persilylated palladacyclopentane, [Pd­(SiC₁₂H₈)₄(dmpe)], with four 1,1-silafluorene units

Dipalladium Complexes with Bridging Monoalkyl or Monophenyl Silyl Ligands in the Solid State and in Solution

HexSiH₃, PhSiH₃, and PhSiClH₂ reacted with [Pd­(PCy₃)₂] to yield dipalladium complexes with bridging silyl ligands: [{Pd­(PCy₃)}₂(μ-HSiXR)₂] (<b>1</b>, R = Hex, X = H; <b>2</b>, R = Ph, X = H; <b>3</b>, R = Ph, X = Cl). The X-ray crystallographic results displayed a typical bis­(silyl)-bridged dinuclear structure with an anti conformation of the substituents on the Si atom in the solid state. Temperature-dependent NMR spectroscopic analyses of <b>1</b> and <b>2</b> revealed a dynamic <i>syn</i>–<i>anti</i> isomerization of the complex via exchange of the bridging and nonbridging Si–H hydrogens in solution. Complex <b>3</b> with bridging chloro­(phenyl)­silyl ligands did not show such a dynamic behavior

Univariate and multivariate analyses of microbiota associated with AILD patients.

<p>Univariate and multivariate analyses of microbiota associated with AILD patients.</p

Correlation between the relative abundance of predominant genera and the levels of immunological biomarkers in the saliva of AILD patients.

<p>Correlation between the relative abundance of predominant genera and the levels of immunological biomarkers in the saliva of AILD patients.</p

Mean genus or order abundance of gut microbiota in the PBC, AIH and HC groups.

<p>The plotted values are the mean abundance of the 8 abundant genera and 1 abundant order in each group. The results are expressed as the mean ± SD. Differences were compared using the Mann-Whitney U-test; *<i>P</i><0.05, **<i>P</i><0.01, ***<i>P</i><0.0005.</p

Correlation between oral microbiota and gut microbiota in AILD patients.

<p>Correlation between oral microbiota and gut microbiota in AILD patients.</p

Principal component analysis (PCA) of the oral and gut microbiota among the 71 T-RFLP profiles.

<p>(a) The T-RFLP profiles were classified into two clusters by hierarchical cluster analysis (orange circle: Cluster I, green circle: Cluster II). (b) Principal component analysis of the oral microbiota in the AILD (blue circle) and HC groups (red circle). (c) Principal component analysis of the gut microbiota in the AILD (blue circle) and HC groups (red circle). (d) Index (Shannon, y-axis) of genera diversity in oral microbiota, (e) Index (Shannon, y-axis) of genera diversity in gut microbiota.</p

Clinical characteristics of HCs and patients with PBC or AIH.

<p>Clinical characteristics of HCs and patients with PBC or AIH.</p

Cytokine levels in the saliva of HCs and patients with PBC or AIH.

<p>The salivary levels of IL-1β (a), IL-8 (b), MIP-1β (c), IgA (d), TNF-α (e), and IFN-γ (f). The results are expressed as the mean ± SD. Differences were compared using the Mann-Whitney U-test; *<i>P</i><0.05, **<i>P</i><0.01, ***<i>P</i><0.005.</p