Synthesis and Structural Characterization of Lithium, Potassium, Magnesium, and Heavier Group 14 Metal Complexes Derived from 2‑Quinolyl-Linked (Thiophosphorano)methane

The synthesis and structural characterization of lithium, magnesium, potassium, and a series of low-valent group 14 metal compounds derived from the novel 2-quinolyl-linked phosphoranosulfide CH₂(^<i>i</i>Pr₂PS)­(C₉H₆N-2) (<b>3</b>) are reported. The monoanionic thiophosphinoyl lithium complex [Li­(Et₂O)­{CH­(^<i>i</i>Pr₂P–S)­(C₉H₆N-2)}]₂ (<b>4</b>) and magnesium complex [Mg­{CH­(^<i>i</i>Pr₂P–S)­(C₉H₆N-2)}₂] (<b>5</b>) have been prepared from the reaction of <b>3</b> with 1 equiv of ^<i>n</i>BuLi or 0.5 equiv of ^<i>n</i>Bu₂Mg in THF. Metathesis of <b>4</b> with 2 equiv of K^<i>t</i>BuO afforded the corresponding polymeric thiophosphinoyl potassium complex [K­{CH­(^<i>i</i>Pr₂P–S)­(C₉H₆N-2)}]_<i>n</i> (<b>6</b>). The metathesis reaction of <b>4</b> with GeCl₂·(dioxane) and PbCl₂ afforded the “open-box” 1,3-digermacyclobutane [Ge­{μ₂-C­(^<i>i</i>Pr₂PS)­(C₉H₆N-2)]₂ (<b>9</b>) and “twisted-step” 1,3-diplumbacyclobutane [Pb­{μ₂-C­(^<i>i</i>Pr₂PS)­(C₉H₆N-2)]₂ (<b>10</b>), respectively. Reaction of <b>3</b> with 1 equiv of M­{N­(SiMe₃)₂}₂ (M = Sn, Pb) afforded the corresponding “open-box” 1,3-distannacyclobutane [Sn­{μ₂-C­(^<i>i</i>Pr₂PS)­(C₉H₆N-2)]₂ (<b>11</b>) and [Pb­{μ₂-C­(^<i>i</i>Pr₂PS)­(C₉H₆N-2)]₂ (<b>12</b>), respectively. The structures of <b>3</b>–<b>6</b> and <b>9</b>–<b>12</b> have been determined by X-ray crystallography

Synthesis and Structural Characterization of Lithium, Potassium, Magnesium, and Heavier Group 14 Metal Complexes Derived from 2‑Quinolyl-Linked (Thiophosphorano)methane

The synthesis and structural characterization of lithium, magnesium, potassium, and a series of low-valent group 14 metal compounds derived from the novel 2-quinolyl-linked phosphoranosulfide CH₂(^<i>i</i>Pr₂PS)­(C₉H₆N-2) (<b>3</b>) are reported. The monoanionic thiophosphinoyl lithium complex [Li­(Et₂O)­{CH­(^<i>i</i>Pr₂P–S)­(C₉H₆N-2)}]₂ (<b>4</b>) and magnesium complex [Mg­{CH­(^<i>i</i>Pr₂P–S)­(C₉H₆N-2)}₂] (<b>5</b>) have been prepared from the reaction of <b>3</b> with 1 equiv of ^<i>n</i>BuLi or 0.5 equiv of ^<i>n</i>Bu₂Mg in THF. Metathesis of <b>4</b> with 2 equiv of K^<i>t</i>BuO afforded the corresponding polymeric thiophosphinoyl potassium complex [K­{CH­(^<i>i</i>Pr₂P–S)­(C₉H₆N-2)}]_<i>n</i> (<b>6</b>). The metathesis reaction of <b>4</b> with GeCl₂·(dioxane) and PbCl₂ afforded the “open-box” 1,3-digermacyclobutane [Ge­{μ₂-C­(^<i>i</i>Pr₂PS)­(C₉H₆N-2)]₂ (<b>9</b>) and “twisted-step” 1,3-diplumbacyclobutane [Pb­{μ₂-C­(^<i>i</i>Pr₂PS)­(C₉H₆N-2)]₂ (<b>10</b>), respectively. Reaction of <b>3</b> with 1 equiv of M­{N­(SiMe₃)₂}₂ (M = Sn, Pb) afforded the corresponding “open-box” 1,3-distannacyclobutane [Sn­{μ₂-C­(^<i>i</i>Pr₂PS)­(C₉H₆N-2)]₂ (<b>11</b>) and [Pb­{μ₂-C­(^<i>i</i>Pr₂PS)­(C₉H₆N-2)]₂ (<b>12</b>), respectively. The structures of <b>3</b>–<b>6</b> and <b>9</b>–<b>12</b> have been determined by X-ray crystallography

Synthesis and Structural Characterization of a Tin Analogue of Allene

The reaction of [MgC­(PPh₂S)₂(THF)]₂ (<b>1</b>; THF = tetrahydrofuran) with 1 equiv of SnCl₄ in THF afforded a novel tin analogue of allene [Sn­{C­(PPh₂S)₂}₂] (<b>2</b>). The structure of compound <b>2</b> has been characterized by X-ray crystallography and NMR spectroscopy

Synthesis and Structural Characterization of Base-Stabilized Oligomeric Heterovinylidenes

Metalation of the (iminophosphoranyl)­phosphine PPh₂CH₂(PPh₂NSiMe₃) (<b>1</b>) with an equimolar amount of <i>n</i>-BuLi afforded the monolithium salt [Li­{CH­(PPh₂)­(PPh₂NSiMe₃)}­(THF)₂] (<b>2</b>). The reaction of <b>2</b> with GeCl₂·1,4-dioxane has led to the formation of a germavinylene moiety, which trimerized to form a new heterocyclic cage compound, [{(PPh₂NSiMe₃)­(PPh₂)­CGe:}­{(PPh₂NSiMe₃)­(PPh₂)­C}₂Ge→Ge:] (<b>3</b>). A similar reaction of the lithium methanide complex <b>2</b> with SnCl₂ afforded the stannavinylidene moiety, which underwent a “head-to-tail” cycloaddition to form a stable 1,3-distannacyclobutane, <b>4</b>. A trapping reaction of <b>4</b> with diiron nonacarbonyl gave the novel iron stannavinylidene complex <b>5</b>. The solid-state structure analysis of <b>5</b> reveals that it contains two stannavinylidene moieties bonded in a Sn–P “head-to-tail” fashion, with one of the tin­(II) centers coordinating to a Fe­(CO)₄ moiety. The X-ray structures of <b>2</b>–<b>5</b> have been determined by X-ray crystallography. In addition, the dynamic behavior of <b>5</b> has been studied by means of variable-temperature ³¹P and ¹¹⁹Sn NMR spectroscopy

Synthesis and Structural Characterization of Metallogermylenes, Cp-Substituted Germylene, and a Germanium(II)-Borane Adduct from Pyridyl-1-azaallyl Germanium(II) Chloride

The reaction of [{N­(SiMe₃)­C­(Ph)­C­(SiMe₃)­(C₅H₄N-2)}­GeCl] (<b>1</b>) with Na­[M­(η⁵-C₅H₅)­(CO)₃]·2DME (M = Mo, W) afforded the metallogermylenes [{N­(SiMe₃)­C­(Ph)­C­(SiMe₃)­(C₅H₄N-2)}­Ge-M­(η⁵-C₅H₅)­(CO)₃] (M = Mo (<b>2</b>), W (<b>3</b>)). Compounds <b>2</b> and <b>3</b> have been characterized by X-ray crystallography and NMR and IR spectroscopy. Structural analyses of compounds <b>2</b> and <b>3</b> are consistent with the presence of lone-pair electrons at the germanium­(II) center. The Ge–Mo and Ge–W bond distances of 2.875(1) and 2.852(1) Å are consistent with Ge–metal single bonds. The chlorogermylene <b>1</b> was also used in the synthesis of a substituted germylene, [{N­(SiMe₃)­C­(Ph)­C­(SiMe₃)­(C₅H₄N-2)}­Ge­(η¹-C₅H₅)] (<b>4</b>), by reaction with sodium cyclopentadienylide. The reaction of compound <b>1</b> with tris­(pentafluorophenyl)­borane led to the formation of a Lewis acid–base adduct, [{N­(SiMe₃)­C­(Ph)­C­(SiMe₃)­(C₅H₄N-2)}­Ge­(Cl)→B­(C₆F₅)₃] (<b>5</b>)

Reactivity of Pyridyl-1-azaallyl Germanium(I) Dimer: Synthesis of a Digermahydrazine Derivative and an Iron-Coordinated Germanium(I) Dimer

Reactivity of the pyridyl-1-azaallyl germanium­(I) dimer LGeGeL (<b>2</b>; L = N­(SiMe₃)­C­(Ph)­C­(SiMe₃)­(C₅H₄N-2)) has been investigated. Treatment of germanium­(I) dimer <b>2</b> with 1 equiv of azobenzene afforded the pyridyl-1-azaallyl digermahydrazine derivative [LGeNPh]₂ (<b>3</b>). The reaction of <b>2</b> with 1 and 2 equiv of diiron nonacarbonyl, Fe₂(CO)₉, afforded the novel unsymmetric germanium­(I) complex [LGeGe­(Fe­(CO)₄)­L] (<b>4</b>) and the diiron Lewis acid–base adduct [LGe­(Fe­(CO)₄)]₂ (<b>5</b>). The solid-state structure of <b>4</b> reveals that the two germanium­(I) centers within the same molecule have different coordinating geometries. Compound <b>4</b> can also be prepared by the facile reaction of the pyridyl-1-azaallyl germanium­(II) chloride LGeCl (<b>1</b>) with Collman’s reagent, Na₂Fe­(CO)₄

Synthesis and Structural Characterization of Metallogermylenes, Cp-Substituted Germylene, and a Germanium(II)-Borane Adduct from Pyridyl-1-azaallyl Germanium(II) Chloride

The reaction of [{N­(SiMe₃)­C­(Ph)­C­(SiMe₃)­(C₅H₄N-2)}­GeCl] (<b>1</b>) with Na­[M­(η⁵-C₅H₅)­(CO)₃]·2DME (M = Mo, W) afforded the metallogermylenes [{N­(SiMe₃)­C­(Ph)­C­(SiMe₃)­(C₅H₄N-2)}­Ge-M­(η⁵-C₅H₅)­(CO)₃] (M = Mo (<b>2</b>), W (<b>3</b>)). Compounds <b>2</b> and <b>3</b> have been characterized by X-ray crystallography and NMR and IR spectroscopy. Structural analyses of compounds <b>2</b> and <b>3</b> are consistent with the presence of lone-pair electrons at the germanium­(II) center. The Ge–Mo and Ge–W bond distances of 2.875(1) and 2.852(1) Å are consistent with Ge–metal single bonds. The chlorogermylene <b>1</b> was also used in the synthesis of a substituted germylene, [{N­(SiMe₃)­C­(Ph)­C­(SiMe₃)­(C₅H₄N-2)}­Ge­(η¹-C₅H₅)] (<b>4</b>), by reaction with sodium cyclopentadienylide. The reaction of compound <b>1</b> with tris­(pentafluorophenyl)­borane led to the formation of a Lewis acid–base adduct, [{N­(SiMe₃)­C­(Ph)­C­(SiMe₃)­(C₅H₄N-2)}­Ge­(Cl)→B­(C₆F₅)₃] (<b>5</b>)