4 research outputs found
Synthesis, Structure, and Reactivity of Tungsten Acetylide–Germylene Complexes
The
novel acetylide–germylene complexes Cp*(CO)<sub>2</sub>W(GePh<sub>2</sub>)(CCR) (<b>7a</b>, R = SiMe<sub>3</sub>; <b>7b</b>, R = CMe<sub>3</sub>) were synthesized by the reactions of Cp*(CO)<sub>2</sub>W(NCMe)Me with Ph<sub>2</sub>HGeCCR (R = SiMe<sub>3</sub>, CMe<sub>3</sub>). X-ray crystal analysis of <b>7a</b> revealed significantly increased germylene–tungsten and decreased
germylene–acetylide interactions in comparison to the corresponding
interactions in the previously reported acetylide–silylene
complex Cp*(CO)<sub>2</sub>W(SiPh<sub>2</sub>)(CCSiMe<sub>3</sub>)
(<b>1</b>). Complexes <b>7a</b>,<b>b</b> reacted
with acetone to give the six-membered cyclic vinylidene complexes
Cp*(CO)<sub>2</sub>WCC(R)CMe<sub>2</sub>OGePh<sub>2</sub> (<b>8a</b>, R = SiMe<sub>3</sub>; <b>8b</b>,
R = CMe<sub>3</sub>) by acetone insertion reaction, similar to the
case of <b>1</b> affording Cp*(CO)<sub>2</sub>WCC(SiMe<sub>3</sub>)CMe<sub>2</sub>OSiPh<sub>2</sub> (<b>2</b>). In the presence of 4-(dimethylamino)pyridine (DMAP),
complexes <b>8a</b>,<b>b</b> gave <i>trans</i>- and <i>cis</i>-DMAP-stabilized germylene acetylide
complexes Cp*(CO)<sub>2</sub>W(GePh<sub>2</sub>·DMAP)(CCR) (<i><b>trans</b></i><b>-</b> and <i><b>cis</b></i><b>-9a</b>, R = SiMe<sub>3</sub>; <i><b>trans</b></i><b>-</b> and <i><b>cis</b></i><b>-9b</b>, R = CMe<sub>3</sub>) and acetone, showing a reactivity
different from that of the silicon analogue <b>2</b>. Complexes <i><b>cis-</b></i><b>9a,b</b> were isolated as crystals
from the reaction of <b>7a,b</b> with DMAP and formed mixtures
with <i><b>trans</b></i><b>-9a,b</b> in solutions, respectively. A mixture of <b><i>cis</i>-</b> and <b><i>trans</i>-9a</b> reacted with acetone to form an equilibrium mixture with <b>8a</b> and DMAP. The reactivity of <b>7a</b>,<b>b</b> toward Me<sub>3</sub>COH was also investigated to
reveal the formation of the vinylidene complexes Cp*(CO)<sub>2</sub>W{GePh<sub>2</sub>(OCMe<sub>3</sub>)}CCHR (<b>10a</b>, R = SiMe<sub>3</sub>; <b>10b</b>, R = CMe<sub>3</sub>); <b>10a</b> is equilibrated with <b>7a</b> and Me<sub>3</sub>COH, whereas <b>10b</b> is further converted to the
carbyne complex Cp*(CO)<sub>2</sub>WCCH(CMe<sub>3</sub>){GePh<sub>2</sub>(OCMe<sub>3</sub>)} (<b>11</b>)
Synthesis, Structure, and Reactivity of Tungsten Acetylide–Germylene Complexes
The
novel acetylide–germylene complexes Cp*(CO)<sub>2</sub>W(GePh<sub>2</sub>)(CCR) (<b>7a</b>, R = SiMe<sub>3</sub>; <b>7b</b>, R = CMe<sub>3</sub>) were synthesized by the reactions of Cp*(CO)<sub>2</sub>W(NCMe)Me with Ph<sub>2</sub>HGeCCR (R = SiMe<sub>3</sub>, CMe<sub>3</sub>). X-ray crystal analysis of <b>7a</b> revealed significantly increased germylene–tungsten and decreased
germylene–acetylide interactions in comparison to the corresponding
interactions in the previously reported acetylide–silylene
complex Cp*(CO)<sub>2</sub>W(SiPh<sub>2</sub>)(CCSiMe<sub>3</sub>)
(<b>1</b>). Complexes <b>7a</b>,<b>b</b> reacted
with acetone to give the six-membered cyclic vinylidene complexes
Cp*(CO)<sub>2</sub>WCC(R)CMe<sub>2</sub>OGePh<sub>2</sub> (<b>8a</b>, R = SiMe<sub>3</sub>; <b>8b</b>,
R = CMe<sub>3</sub>) by acetone insertion reaction, similar to the
case of <b>1</b> affording Cp*(CO)<sub>2</sub>WCC(SiMe<sub>3</sub>)CMe<sub>2</sub>OSiPh<sub>2</sub> (<b>2</b>). In the presence of 4-(dimethylamino)pyridine (DMAP),
complexes <b>8a</b>,<b>b</b> gave <i>trans</i>- and <i>cis</i>-DMAP-stabilized germylene acetylide
complexes Cp*(CO)<sub>2</sub>W(GePh<sub>2</sub>·DMAP)(CCR) (<i><b>trans</b></i><b>-</b> and <i><b>cis</b></i><b>-9a</b>, R = SiMe<sub>3</sub>; <i><b>trans</b></i><b>-</b> and <i><b>cis</b></i><b>-9b</b>, R = CMe<sub>3</sub>) and acetone, showing a reactivity
different from that of the silicon analogue <b>2</b>. Complexes <i><b>cis-</b></i><b>9a,b</b> were isolated as crystals
from the reaction of <b>7a,b</b> with DMAP and formed mixtures
with <i><b>trans</b></i><b>-9a,b</b> in solutions, respectively. A mixture of <b><i>cis</i>-</b> and <b><i>trans</i>-9a</b> reacted with acetone to form an equilibrium mixture with <b>8a</b> and DMAP. The reactivity of <b>7a</b>,<b>b</b> toward Me<sub>3</sub>COH was also investigated to
reveal the formation of the vinylidene complexes Cp*(CO)<sub>2</sub>W{GePh<sub>2</sub>(OCMe<sub>3</sub>)}CCHR (<b>10a</b>, R = SiMe<sub>3</sub>; <b>10b</b>, R = CMe<sub>3</sub>); <b>10a</b> is equilibrated with <b>7a</b> and Me<sub>3</sub>COH, whereas <b>10b</b> is further converted to the
carbyne complex Cp*(CO)<sub>2</sub>WCCH(CMe<sub>3</sub>){GePh<sub>2</sub>(OCMe<sub>3</sub>)} (<b>11</b>)
Reactions of Tungsten Acetylide–Silylene Complexes with Pyridines: Direct Observation of Silylene/Silyl Migration in Tungsten Acetylide and Carbyne/Vinylidene Frameworks
Reaction of acetylide–silylene complex Cp*(CO)<sub>2</sub>W(SiPh<sub>2</sub>)(CC<sup><i>t</i></sup>Bu) (<b>1a</b>) with 4-(dimethylamino)pyridine (DMAP) gave an equilibrium
mixture
of DMAP-stabilized silylene acetylide complexes <i>trans-</i> and <i>cis</i>-Cp*(CO)<sub>2</sub>W(SiPh<sub>2</sub>·DMAP)(CC<sup><i>t</i></sup>Bu) (<i><b>trans</b></i><b>-4</b> and <i><b>cis</b></i><b>-4</b>).
The corresponding reaction using Cp*(CO)<sub>2</sub>W(SiPh<sub>2</sub>)(CCSiMe<sub>3</sub>) (<b>2</b>) produced the novel DMAP-coordinated
silenylcarbyne/silylvinylidene complex Cp*(CO)<sub>2</sub>W[CC(SiPh<sub>2</sub>·DMAP)(SiMe<sub>3</sub>)] (<b>6a</b>) as a major
product, which was equilibrated with <i>trans-</i> and <i>cis</i>-Cp*(CO)<sub>2</sub>W(SiPh<sub>2</sub>·DMAP)(CCSiMe<sub>3</sub>) (<i><b>trans</b></i><b>-5a</b> and <i><b>cis</b></i><b>-5a</b>) via silylene/silyl migration.
The novel structures of <i><b>cis</b></i><b>-4</b> and <b>6a</b> were revealed by X-ray crystallography. A mixture
of <b>2</b> and pyridine exhibited interesting temperature-dependent
NMR spectral changes, indicating the formation of <i>trans-</i> and <i>cis</i>-Cp*(CO)<sub>2</sub>W(SiPh<sub>2</sub>·py)(CCSiMe<sub>3</sub>) (<i><b>trans</b></i><b>-5b</b> and <i><b>cis</b></i><b>-5b</b>) and Cp*(CO)<sub>2</sub>W[CC(SiPh<sub>2</sub>·py)(SiMe<sub>3</sub>)] (<b>6b</b>) at low temperature, while a mixture of <b>1a</b> and pyridine
showed no such spectral changes
Reactions of Tungsten Acetylide–Silylene Complexes with Pyridines: Direct Observation of Silylene/Silyl Migration in Tungsten Acetylide and Carbyne/Vinylidene Frameworks
Reaction of acetylide–silylene complex Cp*(CO)<sub>2</sub>W(SiPh<sub>2</sub>)(CC<sup><i>t</i></sup>Bu) (<b>1a</b>) with 4-(dimethylamino)pyridine (DMAP) gave an equilibrium
mixture
of DMAP-stabilized silylene acetylide complexes <i>trans-</i> and <i>cis</i>-Cp*(CO)<sub>2</sub>W(SiPh<sub>2</sub>·DMAP)(CC<sup><i>t</i></sup>Bu) (<i><b>trans</b></i><b>-4</b> and <i><b>cis</b></i><b>-4</b>).
The corresponding reaction using Cp*(CO)<sub>2</sub>W(SiPh<sub>2</sub>)(CCSiMe<sub>3</sub>) (<b>2</b>) produced the novel DMAP-coordinated
silenylcarbyne/silylvinylidene complex Cp*(CO)<sub>2</sub>W[CC(SiPh<sub>2</sub>·DMAP)(SiMe<sub>3</sub>)] (<b>6a</b>) as a major
product, which was equilibrated with <i>trans-</i> and <i>cis</i>-Cp*(CO)<sub>2</sub>W(SiPh<sub>2</sub>·DMAP)(CCSiMe<sub>3</sub>) (<i><b>trans</b></i><b>-5a</b> and <i><b>cis</b></i><b>-5a</b>) via silylene/silyl migration.
The novel structures of <i><b>cis</b></i><b>-4</b> and <b>6a</b> were revealed by X-ray crystallography. A mixture
of <b>2</b> and pyridine exhibited interesting temperature-dependent
NMR spectral changes, indicating the formation of <i>trans-</i> and <i>cis</i>-Cp*(CO)<sub>2</sub>W(SiPh<sub>2</sub>·py)(CCSiMe<sub>3</sub>) (<i><b>trans</b></i><b>-5b</b> and <i><b>cis</b></i><b>-5b</b>) and Cp*(CO)<sub>2</sub>W[CC(SiPh<sub>2</sub>·py)(SiMe<sub>3</sub>)] (<b>6b</b>) at low temperature, while a mixture of <b>1a</b> and pyridine
showed no such spectral changes