A Silylyne Tungsten Complex Having an Eind Group on Silicon: Its Dimer–Monomer Equilibrium and Cycloaddition Reactions with Carbodiimide and Diaryl Ketones

A tungsten silylyne complex having a fused-ring group (Eind) on Si was synthesized from a hydrido hydrosilylene complex via stepwise abstraction of a proton and a hydride and was isolated as an eight-membered cyclic dimer bound through two isocarbonyl linkages. The IR and variable-temperature NMR analyses revealed that the dimer is in equilibrium with a monomeric silylyne complex in solution. The silylyne complex underwent [2 + 2] cycoaddition reactions with carbodiimide and diaryl ketones, and in the latter case the cycloaddition product further reacted with another molecule of ketone to give a complex formed through C–C and Si–C coupling

A Silylyne Tungsten Complex Having an Eind Group on Silicon: Its Dimer–Monomer Equilibrium and Cycloaddition Reactions with Carbodiimide and Diaryl Ketones

A tungsten silylyne complex having a fused-ring group (Eind) on Si was synthesized from a hydrido hydrosilylene complex via stepwise abstraction of a proton and a hydride and was isolated as an eight-membered cyclic dimer bound through two isocarbonyl linkages. The IR and variable-temperature NMR analyses revealed that the dimer is in equilibrium with a monomeric silylyne complex in solution. The silylyne complex underwent [2 + 2] cycoaddition reactions with carbodiimide and diaryl ketones, and in the latter case the cycloaddition product further reacted with another molecule of ketone to give a complex formed through C–C and Si–C coupling

sj-tiff-3-jet-10.1177_15266028221124727 – Supplemental material for Retrospective Multicenter Comparison Between Viabahn Covered Stent-Grafts and Supera Interwoven Nitinol Stents for Endovascular Treatment in Severely Calcified Femoropopliteal Artery Disease: The ARMADILLO Study (Adjusted Retrospective coMparison of scAffolDs In caLcified LesiOns)

Supplemental material, sj-tiff-3-jet-10.1177_15266028221124727 for Retrospective Multicenter Comparison Between Viabahn Covered Stent-Grafts and Supera Interwoven Nitinol Stents for Endovascular Treatment in Severely Calcified Femoropopliteal Artery Disease: The ARMADILLO Study (Adjusted Retrospective coMparison of scAffolDs In caLcified LesiOns) by Kazunori Horie, Mitsuyoshi Takahara, Tatsuya Nakama, Akiko Tanaka, Kazuki Tobita, Naoki Hayakawa, Shinsuke Mori, Yo Iwata and Kenji Suzuki in Journal of Endovascular Therapy</p

sj-tiff-2-jet-10.1177_15266028221124727 – Supplemental material for Retrospective Multicenter Comparison Between Viabahn Covered Stent-Grafts and Supera Interwoven Nitinol Stents for Endovascular Treatment in Severely Calcified Femoropopliteal Artery Disease: The ARMADILLO Study (Adjusted Retrospective coMparison of scAffolDs In caLcified LesiOns)

Supplemental material, sj-tiff-2-jet-10.1177_15266028221124727 for Retrospective Multicenter Comparison Between Viabahn Covered Stent-Grafts and Supera Interwoven Nitinol Stents for Endovascular Treatment in Severely Calcified Femoropopliteal Artery Disease: The ARMADILLO Study (Adjusted Retrospective coMparison of scAffolDs In caLcified LesiOns) by Kazunori Horie, Mitsuyoshi Takahara, Tatsuya Nakama, Akiko Tanaka, Kazuki Tobita, Naoki Hayakawa, Shinsuke Mori, Yo Iwata and Kenji Suzuki in Journal of Endovascular Therapy</p

Synthesis and Structural Characterization of Lithium and Titanium Complexes Bearing a Bulky Aryloxide Ligand Based on a Rigid Fused-Ring <i>s</i>‑Hydrindacene Skeleton

The bulky aryl alcohols, (Rind)­OH (<b>1</b>) [Rind = EMind (<b>a</b>) and Eind (<b>b</b>)], based on the rigid fused-ring 1,1,3,3,5,5,7,7-octa-R-substituted <i>s</i>-hydrindacene skeleton were prepared by the reaction of (Rind)Li with nitrobenzene followed by protonation. The treatment of <b>1</b> with ^<i>n</i>BuLi affords the lithium aryloxide dimers [(Rind)­O­Li­(THF)]₂ (<b>2</b>) or trimers [(Rind)­OLi]₃ (<b>3</b>), depending on the employed solvents (THF = tetrahydrofuran). The salt metathesis reaction of [(EMind)­O­Li­(THF)]₂ (<b>2a</b>) with TiCl₄(THF)₂ leads to the formation of the mononuclear diamagnetic mono- and bis­(aryloxide) Ti­(IV) complexes, [(EMind)­O]­TiCl₃(THF) (<b>4a</b>) and [(EMind)­O]₂TiCl₂ (<b>5a</b>). We also isolated a trace amount of the tris­(aryloxide) Ti­(IV) complex, [(EMind)­O]₃TiCl (<b>6a</b>). The reaction between <b>2a</b> and TiCl₃(THF)₃ resulted in the isolation of the mononuclear paramagnetic mono- and bis­(aryloxide) Ti­(III) complexes, [(EMind)­O]­TiCl₂(THF)₂ (<b>7a</b>) and [(EMind)­O]₂­TiCl­(THF)₂ (<b>8a</b>). The discrete monomeric structures of the titanium complexes <b>4a</b>, <b>5a</b>, <b>6a</b>, <b>7a</b>, and <b>8a</b> were determined by X-ray crystallography

sj-docx-1-jet-10.1177_15266028221124727 – Supplemental material for Retrospective Multicenter Comparison Between Viabahn Covered Stent-Grafts and Supera Interwoven Nitinol Stents for Endovascular Treatment in Severely Calcified Femoropopliteal Artery Disease: The ARMADILLO Study (Adjusted Retrospective coMparison of scAffolDs In caLcified LesiOns)

Supplemental material, sj-docx-1-jet-10.1177_15266028221124727 for Retrospective Multicenter Comparison Between Viabahn Covered Stent-Grafts and Supera Interwoven Nitinol Stents for Endovascular Treatment in Severely Calcified Femoropopliteal Artery Disease: The ARMADILLO Study (Adjusted Retrospective coMparison of scAffolDs In caLcified LesiOns) by Kazunori Horie, Mitsuyoshi Takahara, Tatsuya Nakama, Akiko Tanaka, Kazuki Tobita, Naoki Hayakawa, Shinsuke Mori, Yo Iwata and Kenji Suzuki in Journal of Endovascular Therapy</p

π‑Conjugation between a SiSi Double Bond and Thiophene Rings: Synthesis, Structural Characteristics, and Photophysical Properties of 1,2-Bis(thiophen-2-yl)disilene and 1,2-Bis(2,2′-bithiophen-5-yl)disilene

The two new disilene compounds, 1,2-bis­(thiophen-2-yl)­disilene (<b>1</b>) and 1,2-bis­(2,2′-bithiophen-5-yl)­disilene (<b>2</b>), supported by the fused-ring bulky Eind groups (Eind = 1,1,3,3,5,5,7,7-octaethyl-<i>s</i>-hydrindacen-4-yl) have been obtained as orange and purple crystals, respectively, by the reduction of the corresponding dibromosilanes. Their X-ray structures and spectroscopic properties demonstrate the effective π-conjugation between a SiSi double bond and thiophene units. Notably, the π-extended <b>2</b> exhibits a distinct emission both in solution and in the solid state at room temperature based on the essentially coplanar 1,2-bis­(bithienyl)­disilene skeleton. The structural features and electronic properties of <b>1</b> and <b>2</b> have been thoroughly characterized both experimentally and computationally

Synthesis and Structural Characterization of Lithium and Titanium Complexes Bearing a Bulky Aryloxide Ligand Based on a Rigid Fused-Ring <i>s</i>‑Hydrindacene Skeleton

The bulky aryl alcohols, (Rind)­OH (<b>1</b>) [Rind = EMind (<b>a</b>) and Eind (<b>b</b>)], based on the rigid fused-ring 1,1,3,3,5,5,7,7-octa-R-substituted <i>s</i>-hydrindacene skeleton were prepared by the reaction of (Rind)Li with nitrobenzene followed by protonation. The treatment of <b>1</b> with ^<i>n</i>BuLi affords the lithium aryloxide dimers [(Rind)­O­Li­(THF)]₂ (<b>2</b>) or trimers [(Rind)­OLi]₃ (<b>3</b>), depending on the employed solvents (THF = tetrahydrofuran). The salt metathesis reaction of [(EMind)­O­Li­(THF)]₂ (<b>2a</b>) with TiCl₄(THF)₂ leads to the formation of the mononuclear diamagnetic mono- and bis­(aryloxide) Ti­(IV) complexes, [(EMind)­O]­TiCl₃(THF) (<b>4a</b>) and [(EMind)­O]₂TiCl₂ (<b>5a</b>). We also isolated a trace amount of the tris­(aryloxide) Ti­(IV) complex, [(EMind)­O]₃TiCl (<b>6a</b>). The reaction between <b>2a</b> and TiCl₃(THF)₃ resulted in the isolation of the mononuclear paramagnetic mono- and bis­(aryloxide) Ti­(III) complexes, [(EMind)­O]­TiCl₂(THF)₂ (<b>7a</b>) and [(EMind)­O]₂­TiCl­(THF)₂ (<b>8a</b>). The discrete monomeric structures of the titanium complexes <b>4a</b>, <b>5a</b>, <b>6a</b>, <b>7a</b>, and <b>8a</b> were determined by X-ray crystallography

Synthesis and Structural Characteristics of Discrete Organoboron and Organoaluminum Hydrides Incorporating Bulky Eind Groups

The bulky Eind-based aryllithium, (Eind)Li (Eind = 1,1,3,3,5,5,7,7-octaethyl-<i>s</i>-hydrindacen-4-yl), reacted with BF₃·OEt₂ in Et₂O to form the corresponding aryldifluoroborane (Eind)­BF₂ (<b>1</b>), along with a trace amount of the sterically congested diarylborane, (Eind)₂BH (<b>2</b>). The reaction of <b>1</b> with LiAlH₄ in THF led to the isolation of the corresponding lithium trihydroborate [Li­(thf)]₂[(Eind)­BH₃]₂ (<b>3</b>), which can be transformed into the diborane(6), (Eind)­HB­(μ-H)₂BH­(Eind) (<b>4</b>), with treatment with Me₃SiCl. The Eind-based lithium trihydroaluminate [Li­(OEt₂)]₂[(Eind)­AlH₃]₂ (<b>5</b>) has been synthesized by the reaction of (Eind)Li with LiAlH₄ in Et₂O. The subsequent addition of Me₃SiCl to a solution of <b>5</b> in toluene produced the dialumane(6), (Eind)­HAl­(μ-H)₂AlH­(Eind) (<b>6</b>), the heavier congener of <b>4</b>. The dialumane(6) <b>6</b> reacted with lithium metal in a mixed solvent of Et₂O and toluene to give the diarylalumane, (Eind)₂AlH (<b>7</b>), via a disproportionation reaction along with the cleavage and recombination of the Al–C bond. The discrete monomeric structures of <b>1</b>, <b>2</b>, and <b>7</b> and dimeric structures of <b>3</b>, <b>4</b>, <b>5</b>, and <b>6</b> have been determined by X-ray crystallography

π‑Conjugation between a SiSi Double Bond and Thiophene Rings: Synthesis, Structural Characteristics, and Photophysical Properties of 1,2-Bis(thiophen-2-yl)disilene and 1,2-Bis(2,2′-bithiophen-5-yl)disilene

The two new disilene compounds, 1,2-bis­(thiophen-2-yl)­disilene (<b>1</b>) and 1,2-bis­(2,2′-bithiophen-5-yl)­disilene (<b>2</b>), supported by the fused-ring bulky Eind groups (Eind = 1,1,3,3,5,5,7,7-octaethyl-<i>s</i>-hydrindacen-4-yl) have been obtained as orange and purple crystals, respectively, by the reduction of the corresponding dibromosilanes. Their X-ray structures and spectroscopic properties demonstrate the effective π-conjugation between a SiSi double bond and thiophene units. Notably, the π-extended <b>2</b> exhibits a distinct emission both in solution and in the solid state at room temperature based on the essentially coplanar 1,2-bis­(bithienyl)­disilene skeleton. The structural features and electronic properties of <b>1</b> and <b>2</b> have been thoroughly characterized both experimentally and computationally