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

Noticiero de Vigo : diario independiente de la mañana: Ano XXI Número 5470 - 1905 agosto 25

Bisgermavinylidene [(Me₃SiNPPh₂)₂CGe→GeC­(PPh₂NSiMe₃)₂] (<b>1</b>) has been used as a source of unstable germavinylidene for the synthesis of a series of heterobinuclear complexes. The reaction of <b>1</b> with stoichiometric amounts of transition metal chlorides MCl₂ (M = Mn, Fe) yielded [(Me₃SiNPPh₂)₂(GeCl)­CMn­(μ-Cl)]₂ (<b>2</b>) and [(Me₃SiNPPh₂)₂(GeCl)­CFeCl] (<b>3</b>), respectively. Treatment of <b>1</b> with Me₃SiN₃ gave the [2 + 3] cycloaddition product [(Me₃SiNPPh₂)₂CGeN­(SiMe₃)­NN] (<b>4</b>). While similar reaction of <b>1</b> with (^<i>n</i>Bu)₃SnN₃ (^<i>n</i>Bu = <i>n</i>-butyl) and water-borane adduct H₂O → B­(C₆F₅)₃ afforded the 1,2-addition products [(Me₃SiNPPh₂)­{(^<i>n</i>Bu)₃Sn}­CPPh₂NSiMe₃GeN₃] (<b>5</b>) and [HC­(PPh₂NSiMe₃)₂Ge­(OH)­B­(C₆F₅)₃] (<b>6</b>), respectively. The results suggested that the germanium–carbon bond in germavinylidene is capable of forming addition reaction products. The X-ray structures of <b>2</b>–<b>6</b> have been determined

Synthesis of Hetero-Binuclear Complexes from Bisgermavinylidene

Bisgermavinylidene [(Me₃SiNPPh₂)₂CGe→GeC­(PPh₂NSiMe₃)₂] (<b>1</b>) has been used as a source of unstable germavinylidene for the synthesis of a series of heterobinuclear complexes. The reaction of <b>1</b> with stoichiometric amounts of transition metal chlorides MCl₂ (M = Mn, Fe) yielded [(Me₃SiNPPh₂)₂(GeCl)­CMn­(μ-Cl)]₂ (<b>2</b>) and [(Me₃SiNPPh₂)₂(GeCl)­CFeCl] (<b>3</b>), respectively. Treatment of <b>1</b> with Me₃SiN₃ gave the [2 + 3] cycloaddition product [(Me₃SiNPPh₂)₂CGeN­(SiMe₃)­NN] (<b>4</b>). While similar reaction of <b>1</b> with (^<i>n</i>Bu)₃SnN₃ (^<i>n</i>Bu = <i>n</i>-butyl) and water-borane adduct H₂O → B­(C₆F₅)₃ afforded the 1,2-addition products [(Me₃SiNPPh₂)­{(^<i>n</i>Bu)₃Sn}­CPPh₂NSiMe₃GeN₃] (<b>5</b>) and [HC­(PPh₂NSiMe₃)₂Ge­(OH)­B­(C₆F₅)₃] (<b>6</b>), respectively. The results suggested that the germanium–carbon bond in germavinylidene is capable of forming addition reaction products. The X-ray structures of <b>2</b>–<b>6</b> have been determined

Reactivity Study of a Pyridyl-1-azaallylgermanium(I) Dimer: Synthesis of Heavier Ether and Ester Analogues of Germanium

The reactivity study of a pyridyl-1-azaallylgermanium­(I) dimer LGe–GeL [<b>1</b>; L = N­(SiMe₃)­C­(Ph)­C­(SiMe₃)­(C₅H₄N-2)] with different stoichiometric ratios of elemental selenium and tellurium is described. The reactions of <b>1</b> with 1 equiv of selenium and tellurium afforded the first examples of heavier ether analogues of germanium, bis­(germylene) selenide and telluride LGe­(μ-E)­GeL [E = Se (<b>2</b>) and Te (<b>3</b>)], respectively. Meanwhile, the reactions of <b>1</b> with 2 equiv of selenium and tellurium gave the heavier ester analogues LGeE­(μ-E)­GeL [E = Se (<b>4</b>) and (<b>5</b>)]. All compounds have been characterized by X-ray crystallography and multinuclear NMR spectroscopy

Synthesis of Hetero-Binuclear Complexes from Bisgermavinylidene

Bisgermavinylidene [(Me₃SiNPPh₂)₂CGe→GeC­(PPh₂NSiMe₃)₂] (<b>1</b>) has been used as a source of unstable germavinylidene for the synthesis of a series of heterobinuclear complexes. The reaction of <b>1</b> with stoichiometric amounts of transition metal chlorides MCl₂ (M = Mn, Fe) yielded [(Me₃SiNPPh₂)₂(GeCl)­CMn­(μ-Cl)]₂ (<b>2</b>) and [(Me₃SiNPPh₂)₂(GeCl)­CFeCl] (<b>3</b>), respectively. Treatment of <b>1</b> with Me₃SiN₃ gave the [2 + 3] cycloaddition product [(Me₃SiNPPh₂)₂CGeN­(SiMe₃)­NN] (<b>4</b>). While similar reaction of <b>1</b> with (^<i>n</i>Bu)₃SnN₃ (^<i>n</i>Bu = <i>n</i>-butyl) and water-borane adduct H₂O → B­(C₆F₅)₃ afforded the 1,2-addition products [(Me₃SiNPPh₂)­{(^<i>n</i>Bu)₃Sn}­CPPh₂NSiMe₃GeN₃] (<b>5</b>) and [HC­(PPh₂NSiMe₃)₂Ge­(OH)­B­(C₆F₅)₃] (<b>6</b>), respectively. The results suggested that the germanium–carbon bond in germavinylidene is capable of forming addition reaction products. The X-ray structures of <b>2</b>–<b>6</b> have been determined

Synthesis of Hetero-Binuclear Complexes from Bisgermavinylidene

Bisgermavinylidene [(Me₃SiNPPh₂)₂CGe→GeC­(PPh₂NSiMe₃)₂] (<b>1</b>) has been used as a source of unstable germavinylidene for the synthesis of a series of heterobinuclear complexes. The reaction of <b>1</b> with stoichiometric amounts of transition metal chlorides MCl₂ (M = Mn, Fe) yielded [(Me₃SiNPPh₂)₂(GeCl)­CMn­(μ-Cl)]₂ (<b>2</b>) and [(Me₃SiNPPh₂)₂(GeCl)­CFeCl] (<b>3</b>), respectively. Treatment of <b>1</b> with Me₃SiN₃ gave the [2 + 3] cycloaddition product [(Me₃SiNPPh₂)₂CGeN­(SiMe₃)­NN] (<b>4</b>). While similar reaction of <b>1</b> with (^<i>n</i>Bu)₃SnN₃ (^<i>n</i>Bu = <i>n</i>-butyl) and water-borane adduct H₂O → B­(C₆F₅)₃ afforded the 1,2-addition products [(Me₃SiNPPh₂)­{(^<i>n</i>Bu)₃Sn}­CPPh₂NSiMe₃GeN₃] (<b>5</b>) and [HC­(PPh₂NSiMe₃)₂Ge­(OH)­B­(C₆F₅)₃] (<b>6</b>), respectively. The results suggested that the germanium–carbon bond in germavinylidene is capable of forming addition reaction products. The X-ray structures of <b>2</b>–<b>6</b> have been determined

Synthesis of Hetero-Binuclear Complexes from Bisgermavinylidene

Bisgermavinylidene [(Me₃SiNPPh₂)₂CGe→GeC­(PPh₂NSiMe₃)₂] (<b>1</b>) has been used as a source of unstable germavinylidene for the synthesis of a series of heterobinuclear complexes. The reaction of <b>1</b> with stoichiometric amounts of transition metal chlorides MCl₂ (M = Mn, Fe) yielded [(Me₃SiNPPh₂)₂(GeCl)­CMn­(μ-Cl)]₂ (<b>2</b>) and [(Me₃SiNPPh₂)₂(GeCl)­CFeCl] (<b>3</b>), respectively. Treatment of <b>1</b> with Me₃SiN₃ gave the [2 + 3] cycloaddition product [(Me₃SiNPPh₂)₂CGeN­(SiMe₃)­NN] (<b>4</b>). While similar reaction of <b>1</b> with (^<i>n</i>Bu)₃SnN₃ (^<i>n</i>Bu = <i>n</i>-butyl) and water-borane adduct H₂O → B­(C₆F₅)₃ afforded the 1,2-addition products [(Me₃SiNPPh₂)­{(^<i>n</i>Bu)₃Sn}­CPPh₂NSiMe₃GeN₃] (<b>5</b>) and [HC­(PPh₂NSiMe₃)₂Ge­(OH)­B­(C₆F₅)₃] (<b>6</b>), respectively. The results suggested that the germanium–carbon bond in germavinylidene is capable of forming addition reaction products. The X-ray structures of <b>2</b>–<b>6</b> have been determined

Oxo-Bridged Bis(group 4 metal unsymmetric phosphonium-stabilized carbene) Complexes

The synthesis and reactivity of oxo-bridged bis­(group 4 metal unsymmetric phosphonium-stabilized carbene) complexes are described. The reaction of [CH₂R^NR^S] (<b>1</b>; R^N = PPh₂NSiMe₃, R^S = PPh₂S) with 1 equiv of [M­(NMe₂)₄] (M = Zr, Hf) afforded the group 4 metal unsymmetric phosphonium-stabilized carbene complexes [M­(NMe₂)₂(CR^NR^S)] (M = Zr (<b>4</b>), Hf (<b>5</b>)). Their reactions with water in toluene afforded the oxo-bridged derivatives O­[M­(NMe₂)­(CR^NR^S)]₂ (M = Zr (<b>6</b>), Hf (<b>7</b>)). Compound <b>6</b> underwent an insertion reaction with AdNCO to form O­[Zr­{OC­(NMe₂)­NAd}­(CR^NR^S)]₂ (<b>8</b>; Ad = adamantyl). Compounds <b>4</b>–<b>8</b> were characterized by NMR spectroscopy and X-ray crystallography