Bis(<i>m</i>‑terphenyl)silanes

The synthesis and full characterization of the first bis­(<i>m</i>-terphenyl)­silanes, namely, (2,6-Mes₂C₆H₃)₂SiF₂, (2,6-Mes₂C₆H₃)₂SiHF, and (2,6-Mes₂C₆H₃)₂SiH₂, is reported

<i>Peri</i>-Substituted (Ace)Naphthylphosphinoboranes. (Frustrated) Lewis Pairs

The synthesis and molecular structures of 1-(diphenylphosphino)-8-naphthyldimesitylborane (<b>1</b>) and 5-(diphenylphosphino)-6-acenaphthyldimesitylborane (<b>2</b>) are reported. The experimentally determined P–B <i>peri</i> distances of 2.162(2) and 3.050(3) Å allow <b>1</b> and <b>2</b> to be classified as regular and frustrated Lewis pairs. The electronic characteristics of the (non)­bonding P–B contacts are determined by analysis of a set of real-space bonding indicators (RSBIs) derived from the theoretically calculated electron and pair densities. These densities are analyzed utilizing the atoms-in-molecules (AIM), stockholder, and electron-localizability-indicator (ELI-D) space partitioning schemes. The recently introduced mapping of the electron localizability on the ELI-D basin surfaces is also applied. All RSBIs clearly discriminate the bonding P–B contact in <b>1</b> from the nonbonding P–B contact in <b>2</b>, which is due to the fact that the acenaphthene framework is rather rigid, whereas the naphthyl framework shows sufficient conformational flexibility, allowing shorter <i>peri</i> interations. The results are compared to the previously known prototypical phosphinoborane Ph₃PB­(C₆F₅)₃, which serves as a reference for a bonding P–B interaction. The most prominent features of the nonbonding P–B contact in <b>2</b> are the lack of an AIM bond critical point, the unaffected Hirshfeld surfaces of the P and B atomic fragments, and the negligible penetration of the electron population of the ELI-D lone pair basin of the P atom into the AIM B atomic basin

Intramolecularly Coordinated (6-(Diphenylphosphino)acenaphth-5-yl)stannanes. Repulsion vs Attraction of P- and Sn-Containing Substituents in the <i>peri</i> Positions

The intramolecularly coordinated (6-(diphenylphosphino)­acenaphth-5-yl)­stannanes ArSnBu₃ (<b>1</b>), ArSnPh₃ (<b>2</b>), ArSnPh₂Cl (<b>3</b>), ArSnPhCl₂ (<b>4</b>), ArSnCl₃ (<b>5</b>), Ar₂SnCl₂ (<b>6</b>), ArSnPh₂O₃SCF₃ (<b>7</b>), and ArSnPh₂F (<b>8</b>) were synthesized and fully characterized by multinuclear NMR spectroscopy (¹¹⁹Sn, ³¹P, ¹⁹F, ¹³C, ¹H) and X-ray crystallography (Ar = 6-Ph₂P-Ace-5-). Due to the different substituents, the Lewis acidities of the Sn atoms of <b>1</b>–<b>8</b> vary substantially, which is reflected in the different P–Sn <i>peri</i> distances lying in the range from 2.7032(9) to 3.332(2) Å. In MeCN, <b>7</b> undergoes electrolytic dissociation into solvated triarylstannyl cations and triflate anions. The gas-phase structures of <b>2</b>–<b>5</b>, <b>8</b>, and the triarylstannyl cations ArPh₂Sn⁺ (<b>7a</b>) and [ArPh₂Sn·NCMe]⁺ (<b>7b</b>) were obtained by geometry optimization at the B3PW91/TZ level of theory. A detailed analysis of a set of real-space bonding indicators (RSBI) derived from the electron and pair densities following the atoms in molecules (AIM) and electron localizability indicator (ELI-D) topological approaches, respectively, uncovers the Sn–P <i>peri</i> interaction in <b>2</b> to be in the border regime between nonbonding and weakly ionic. With an increasing number of Cl atoms attached to the Sn atom, the Sn–P bond becomes considerably shorter and exhibits a decreasingly polar covalent interaction. As expected, this trend is significantly enhanced for the Sn–P interactions in the charged compounds <b>7a</b>,<b>b</b>. The Sn–P bond properties of <b>8</b>, however, very much resemble those of <b>3</b>, which means that the electronic impact of the F atom in the axial position is comparable to that of the axial Cl atom

Sterically Congested 5‑Diphenylphosphinoacenaphth-6-yl-silanes and -silanols

The synthesis and characterization of the 5-diphenylphosphinoacenaphth-6-yl-silanes 5-Ph₂P-Ace-6-SiMe₂H (<b>1</b>), 5-Ph₂P­(S)-Ace-6-SiMe₂H (<b>1S</b>), 5-Ph₂P­(Se)-Ace-6-SiMe₂H (<b>1Se</b>), and 5-Ph₂P-Ace-6-SiMe₂Cl (<b>2</b>) as well as of the 5-diphenylphosphinoacenaphth-6-yl-silanols 5-Ph₂P-Ace-6-SiMe₂OH (<b>3</b>), 5-Ph₂P­(O)-Ace-6-SiMe₂OH (<b>3O</b>), 5-Ph₂P­(S)-Ace-6-SiMe₂OH (<b>3S</b>), and 5-Ph₂P­(Se)-Ace-6-SiMe₂OH (<b>3Se</b>) are reported. Due to steric congestion in the bay area, the substituents in <i>peri</i>-positions are affected by repulsion, out-of-plane deflection, and distortion of the spatial arrangement to various extents. The <i>peri</i>-interaction energy associated with the steric congestion of these and a number of previously known reference compounds was computationally estimated with a set of isodesmic reactions. The organo-H-silanes <b>1</b>, <b>1S</b>, and <b>1Se</b> possess very weak intramolecular hydrogen bridges of the types Si–H···P and Si–H···EP (E = S, Se), whereas the organosilanols <b>3O</b>, <b>3S</b>, and <b>3Se</b> contain medium-strength hydrogen bonds of the type Si–OH···EP (E = O, S, Se). These hydrogen bonds and those of related model complexes H₃SiOH···(E)­PH₃ were analyzed applying real-space bonding indicators derived from the electron and pair densities using the atoms-in-molecules and electron localizability indicator space-partitioning schemes as well as natural population analysis and natural bond orbital analyses

6‑Diphenylphosphinoacenaphth-5-yl-mercurials as Ligands for d¹⁰ Metals. Observation of Closed-Shell Interactions of the Type Hg(II)···M; M = Hg(II), Ag(I), Au(I)

The salt metathesis reaction of ArLi with HgCl₂ produced Ar₂Hg (<b>1,</b> Ar = 6-Ph₂P-Ace-5), which underwent complex formation with d¹⁰-configurated transition metal chlorides and triflates to give the complexes <b>1</b>·HgCl₂, <b>1</b>·Hg­(O₃SCF₃)₂, <b>1</b>·AgCl, <b>1</b>·Ag­(O₃SCF₃), [<b>1</b>·Ag­(NCMe)₂]­(O₃SCF₃), <b>1</b>·AuCl, and [<b>1</b>·Au]­(O₃SCF₃) comprising significant metallophilic interactions between Hg­(II) and Hg­(II), Ag­(I), and Au­(I), respectively. The transmetalation reaction of ArSnBu₃ with HgCl₂ afforded ArHgCl (<b>2</b>) that also forms a complex with additional HgCl₂, namely, <b>2</b>·HgCl₂, which however lacks metallophilic interactions. Compounds <b>2</b> and <b>1</b>·HgCl₂ possess the same elemental composition and can be interconverted in solution by choice of the solvent. In the presence of tetrahydrothiophene (tht), the complexes <b>1</b>·AuCl and [<b>1</b>·Au]­(O₃SCF₃) underwent rearrangement into the Au­(III) cation [<i>cis</i>-Ar₂Au]⁺ ([<b>3</b>]⁺, which was isolated as Cl^– and (O₃SCF₃)⁻ salts) and elemental Hg. The reaction of <b>1</b>·Hg­(O₃SCF₃)₂ with ArH produced the complex ArHg­(ArH)­(O₃SCF₃) (<b>4</b>). The metallophilic interactions are theoretically analyzed by a set of real-space bonding indicators derived from the atoms-in-molecules (AIM) and electron localizability indicator (ELI) space-partitioning schemes

<i>Peri</i>-Substituted (Ace)Naphthylphosphinoboranes. (Frustrated) Lewis Pairs

The synthesis and molecular structures of 1-(diphenylphosphino)-8-naphthyldimesitylborane (<b>1</b>) and 5-(diphenylphosphino)-6-acenaphthyldimesitylborane (<b>2</b>) are reported. The experimentally determined P–B <i>peri</i> distances of 2.162(2) and 3.050(3) Å allow <b>1</b> and <b>2</b> to be classified as regular and frustrated Lewis pairs. The electronic characteristics of the (non)­bonding P–B contacts are determined by analysis of a set of real-space bonding indicators (RSBIs) derived from the theoretically calculated electron and pair densities. These densities are analyzed utilizing the atoms-in-molecules (AIM), stockholder, and electron-localizability-indicator (ELI-D) space partitioning schemes. The recently introduced mapping of the electron localizability on the ELI-D basin surfaces is also applied. All RSBIs clearly discriminate the bonding P–B contact in <b>1</b> from the nonbonding P–B contact in <b>2</b>, which is due to the fact that the acenaphthene framework is rather rigid, whereas the naphthyl framework shows sufficient conformational flexibility, allowing shorter <i>peri</i> interations. The results are compared to the previously known prototypical phosphinoborane Ph₃PB­(C₆F₅)₃, which serves as a reference for a bonding P–B interaction. The most prominent features of the nonbonding P–B contact in <b>2</b> are the lack of an AIM bond critical point, the unaffected Hirshfeld surfaces of the P and B atomic fragments, and the negligible penetration of the electron population of the ELI-D lone pair basin of the P atom into the AIM B atomic basin

<i>Peri</i>-Substituted (Ace)Naphthylphosphinoboranes. (Frustrated) Lewis Pairs

The synthesis and molecular structures of 1-(diphenylphosphino)-8-naphthyldimesitylborane (<b>1</b>) and 5-(diphenylphosphino)-6-acenaphthyldimesitylborane (<b>2</b>) are reported. The experimentally determined P–B <i>peri</i> distances of 2.162(2) and 3.050(3) Å allow <b>1</b> and <b>2</b> to be classified as regular and frustrated Lewis pairs. The electronic characteristics of the (non)­bonding P–B contacts are determined by analysis of a set of real-space bonding indicators (RSBIs) derived from the theoretically calculated electron and pair densities. These densities are analyzed utilizing the atoms-in-molecules (AIM), stockholder, and electron-localizability-indicator (ELI-D) space partitioning schemes. The recently introduced mapping of the electron localizability on the ELI-D basin surfaces is also applied. All RSBIs clearly discriminate the bonding P–B contact in <b>1</b> from the nonbonding P–B contact in <b>2</b>, which is due to the fact that the acenaphthene framework is rather rigid, whereas the naphthyl framework shows sufficient conformational flexibility, allowing shorter <i>peri</i> interations. The results are compared to the previously known prototypical phosphinoborane Ph₃PB­(C₆F₅)₃, which serves as a reference for a bonding P–B interaction. The most prominent features of the nonbonding P–B contact in <b>2</b> are the lack of an AIM bond critical point, the unaffected Hirshfeld surfaces of the P and B atomic fragments, and the negligible penetration of the electron population of the ELI-D lone pair basin of the P atom into the AIM B atomic basin

Intramolecularly Coordinated (6-(Diphenylphosphino)acenaphth-5-yl)stannanes. Repulsion vs Attraction of P- and Sn-Containing Substituents in the <i>peri</i> Positions

The intramolecularly coordinated (6-(diphenylphosphino)­acenaphth-5-yl)­stannanes ArSnBu₃ (<b>1</b>), ArSnPh₃ (<b>2</b>), ArSnPh₂Cl (<b>3</b>), ArSnPhCl₂ (<b>4</b>), ArSnCl₃ (<b>5</b>), Ar₂SnCl₂ (<b>6</b>), ArSnPh₂O₃SCF₃ (<b>7</b>), and ArSnPh₂F (<b>8</b>) were synthesized and fully characterized by multinuclear NMR spectroscopy (¹¹⁹Sn, ³¹P, ¹⁹F, ¹³C, ¹H) and X-ray crystallography (Ar = 6-Ph₂P-Ace-5-). Due to the different substituents, the Lewis acidities of the Sn atoms of <b>1</b>–<b>8</b> vary substantially, which is reflected in the different P–Sn <i>peri</i> distances lying in the range from 2.7032(9) to 3.332(2) Å. In MeCN, <b>7</b> undergoes electrolytic dissociation into solvated triarylstannyl cations and triflate anions. The gas-phase structures of <b>2</b>–<b>5</b>, <b>8</b>, and the triarylstannyl cations ArPh₂Sn⁺ (<b>7a</b>) and [ArPh₂Sn·NCMe]⁺ (<b>7b</b>) were obtained by geometry optimization at the B3PW91/TZ level of theory. A detailed analysis of a set of real-space bonding indicators (RSBI) derived from the electron and pair densities following the atoms in molecules (AIM) and electron localizability indicator (ELI-D) topological approaches, respectively, uncovers the Sn–P <i>peri</i> interaction in <b>2</b> to be in the border regime between nonbonding and weakly ionic. With an increasing number of Cl atoms attached to the Sn atom, the Sn–P bond becomes considerably shorter and exhibits a decreasingly polar covalent interaction. As expected, this trend is significantly enhanced for the Sn–P interactions in the charged compounds <b>7a</b>,<b>b</b>. The Sn–P bond properties of <b>8</b>, however, very much resemble those of <b>3</b>, which means that the electronic impact of the F atom in the axial position is comparable to that of the axial Cl atom

Probing Donor–Acceptor Interactions in <i>peri</i>-Substituted Diphenylphosphinoacenaphthyl–Element Dichlorides of Group 13 and 15 Elements

Transmetalation reactions of ArLi with ECl₃ (E = Al, P, In, Bi) and ArSnBu₃ with ECl₃ (E = B, Ga, Tl, As, Sb) gave rise to the formation of <i>peri</i>-substituted diphenylphosphinoacenaphthyl–element dichlorides ArECl₂ (Ar = 6-Ph₂P-Ace-5-), which were characterized by multinuclear NMR spectroscopy and X-ray crystallography. DFT calculations were performed on the compounds at relaxed gas-phase molecular geometries. For the series ArECl₂ containing group 13 elements one structure type featuring regular Lewis pairs with short E–P <i>peri</i> distances (E = B, Al, Ga, In, Tl) was observed. For the series ArECl₂ containing group 15 elements two structural types with very different <i>peri</i> distances (E = P, As, Sb, Bi) were found. The computed electron and pair densities were topologically analyzed according to the atoms-in-molecules (AIM) and electron localizability indicator (ELI-D) space-partitioning schemes, which facilitates the characterization of the <i>peri</i> interactions and also allows for monitoring minute electronic effects induced by different substituents and/or spatial arrangements

Depolymerization of Aryltellurinic Anhydrides with Sodium Hydroxide. Synthesis and Structure of the Hydrated Sodium Aryltellurinates [Na(H₂O)₄](RTeO₂) (R = 4-MeOC₆H₄, 8-Me₂NC₁₀H₆)

Depolymerization of the aryltellurinic anhydrides [(RTe)₂O₃]_<i>n</i> (<b>9</b>, R = 4-MeOC₆H₄; <b>6</b>, R = 8-Me₂NC₁₀H₆) with aqueous NaOH afforded the hydrated sodium aryltellurinates [Na­(H₂O)₄]­(4-MeOC₆H₄TeO₂) (<b>10</b>) and [Na­(H₂O)₄]­(8-Me₂NC₁₀H₆TeO₂)·H₂O (<b>11</b>·H₂O) as highly crystalline materials