3 research outputs found
Cooperative Bond Activation Reactions with Ruthenium Carbene Complex PhSO<sub>2</sub>(Ph<sub>2</sub>PNSiMe<sub>3</sub>)CRu(<i>p</i>‑cymene): RuC and N–Si Bond Reactivity
The synthesis of ruthenium carbene
complex PhSO<sub>2</sub>(Ph<sub>2</sub>PNSiMe<sub>3</sub>)ÂCî—»RuÂ(<i>p</i>-cymene)
(<b>3</b>) and its application in cooperative bond activation
reactions were studied. Compound <b>3</b> is accessible via
salt metathesis using the dilithium methandiide ligand or alternatively
via dehydrohalogenation of the corresponding chlorido complex <b>2</b>. The carbene complex was studied by X-ray crystallography,
multielement NMR spectroscopy, and DFT studies, all of which confirm
the presence of a Ruî—»C double bond. The polarization of the
Ruî—»C bond is less pronounced than in an analogous carbene complex
with a thiophosphoryl instead of the iminophosphoryl moiety. This
should be beneficial for realizing reversible activation processes
by the addition of element-hydrogen bonds across the Ruî—»C double
bond. Accordingly, <b>3</b> is more stable and the Ruî—»C
linkage less reactive in the activation of aromatic alcohols and elemental
dihydrogen, showing reversible processes and longer reaction times.
Despite the selective addition of dihydrogen across the Ru–C
bond, the activation of O–H bonds was accompanied by hydrolysis
of the N–Si linkage. The reaction of <b>3</b> with water
led to the hydrolysis of the N–Si bond as well as protonative
cleavage of the central P–C bond in the ligand backbone, thus
resulting in the formation of an unusual dinuclear ruthenium–imido
complex
Cooperative Bond Activation Reactions with Ruthenium Carbene Complex PhSO<sub>2</sub>(Ph<sub>2</sub>PNSiMe<sub>3</sub>)CRu(<i>p</i>‑cymene): RuC and N–Si Bond Reactivity
The synthesis of ruthenium carbene
complex PhSO<sub>2</sub>(Ph<sub>2</sub>PNSiMe<sub>3</sub>)ÂCî—»RuÂ(<i>p</i>-cymene)
(<b>3</b>) and its application in cooperative bond activation
reactions were studied. Compound <b>3</b> is accessible via
salt metathesis using the dilithium methandiide ligand or alternatively
via dehydrohalogenation of the corresponding chlorido complex <b>2</b>. The carbene complex was studied by X-ray crystallography,
multielement NMR spectroscopy, and DFT studies, all of which confirm
the presence of a Ruî—»C double bond. The polarization of the
Ruî—»C bond is less pronounced than in an analogous carbene complex
with a thiophosphoryl instead of the iminophosphoryl moiety. This
should be beneficial for realizing reversible activation processes
by the addition of element-hydrogen bonds across the Ruî—»C double
bond. Accordingly, <b>3</b> is more stable and the Ruî—»C
linkage less reactive in the activation of aromatic alcohols and elemental
dihydrogen, showing reversible processes and longer reaction times.
Despite the selective addition of dihydrogen across the Ru–C
bond, the activation of O–H bonds was accompanied by hydrolysis
of the N–Si linkage. The reaction of <b>3</b> with water
led to the hydrolysis of the N–Si bond as well as protonative
cleavage of the central P–C bond in the ligand backbone, thus
resulting in the formation of an unusual dinuclear ruthenium–imido
complex
Cooperative Bond Activation Reactions with Ruthenium Carbene Complex PhSO<sub>2</sub>(Ph<sub>2</sub>PNSiMe<sub>3</sub>)CRu(<i>p</i>‑cymene): RuC and N–Si Bond Reactivity
The synthesis of ruthenium carbene
complex PhSO<sub>2</sub>(Ph<sub>2</sub>PNSiMe<sub>3</sub>)ÂCî—»RuÂ(<i>p</i>-cymene)
(<b>3</b>) and its application in cooperative bond activation
reactions were studied. Compound <b>3</b> is accessible via
salt metathesis using the dilithium methandiide ligand or alternatively
via dehydrohalogenation of the corresponding chlorido complex <b>2</b>. The carbene complex was studied by X-ray crystallography,
multielement NMR spectroscopy, and DFT studies, all of which confirm
the presence of a Ruî—»C double bond. The polarization of the
Ruî—»C bond is less pronounced than in an analogous carbene complex
with a thiophosphoryl instead of the iminophosphoryl moiety. This
should be beneficial for realizing reversible activation processes
by the addition of element-hydrogen bonds across the Ruî—»C double
bond. Accordingly, <b>3</b> is more stable and the Ruî—»C
linkage less reactive in the activation of aromatic alcohols and elemental
dihydrogen, showing reversible processes and longer reaction times.
Despite the selective addition of dihydrogen across the Ru–C
bond, the activation of O–H bonds was accompanied by hydrolysis
of the N–Si linkage. The reaction of <b>3</b> with water
led to the hydrolysis of the N–Si bond as well as protonative
cleavage of the central P–C bond in the ligand backbone, thus
resulting in the formation of an unusual dinuclear ruthenium–imido
complex