Organolanthanide-Catalyzed Dehydrogenative Coupling of Silanes. Mechanistic Implications

Craig M. Forsyth; Steven P. Nolan; Tobin Jay Marks

doi:10.1021/om00054a008

Organolanthanide-Catalyzed Dehydrogenative Coupling of Silanes. Mechanistic Implications

Craig M. Forsyth, Steven P. Nolan, Tobin Jay Marks^*

^*Corresponding author for this work

Chemistry

Research output: Contribution to journal › Article › peer-review

104 Scopus citations

Abstract

Organolanthanide complexes of the type Cp’₂LnR (Cp’ = η⁵-Me₅C₅; Ln = La, Nd, Sm, Y, Lu; R = H, CH(SiMe₃)₂), Me₂SiCp″₂LnR (Cp″ = η⁵-Me₄C₅; Ln = Nd; R = CH(SiMe₃)₂), Cp’₂Sm, and Cp’₂Sm(THF)₂ catalyze the rapid dehydrogenative oligomerization of PhSiH₃. Kinetic and mechanistic arguments exclude the importance of metal-centered redox processes in the catalytic cycle and support instead “four-center” “heterolytic” bond-scission/bond-forming sequences.

Original language	English (US)
Pages (from-to)	2543-2545
Number of pages	3
Journal	Organometallics
Volume	10
Issue number	8
DOIs	https://doi.org/10.1021/om00054a008
State	Published - Aug 1 1991

ASJC Scopus subject areas

Physical and Theoretical Chemistry
Organic Chemistry
Inorganic Chemistry

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title = "Organolanthanide-Catalyzed Dehydrogenative Coupling of Silanes. Mechanistic Implications",

abstract = "Organolanthanide complexes of the type Cp{\textquoteright}2LnR (Cp{\textquoteright} = η5-Me5C5; Ln = La, Nd, Sm, Y, Lu; R = H, CH(SiMe3)2), Me2SiCp″2LnR (Cp″ = η5-Me4C5; Ln = Nd; R = CH(SiMe3)2), Cp{\textquoteright}2Sm, and Cp{\textquoteright}2Sm(THF)2 catalyze the rapid dehydrogenative oligomerization of PhSiH3. Kinetic and mechanistic arguments exclude the importance of metal-centered redox processes in the catalytic cycle and support instead “four-center” “heterolytic” bond-scission/bond-forming sequences.",

author = "Forsyth, {Craig M.} and Nolan, {Steven P.} and Marks, {Tobin Jay}",

year = "1991",

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doi = "10.1021/om00054a008",

language = "English (US)",

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journal = "Organometallics",

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T1 - Organolanthanide-Catalyzed Dehydrogenative Coupling of Silanes. Mechanistic Implications

AU - Forsyth, Craig M.

AU - Nolan, Steven P.

AU - Marks, Tobin Jay

PY - 1991/8/1

Y1 - 1991/8/1

N2 - Organolanthanide complexes of the type Cp’2LnR (Cp’ = η5-Me5C5; Ln = La, Nd, Sm, Y, Lu; R = H, CH(SiMe3)2), Me2SiCp″2LnR (Cp″ = η5-Me4C5; Ln = Nd; R = CH(SiMe3)2), Cp’2Sm, and Cp’2Sm(THF)2 catalyze the rapid dehydrogenative oligomerization of PhSiH3. Kinetic and mechanistic arguments exclude the importance of metal-centered redox processes in the catalytic cycle and support instead “four-center” “heterolytic” bond-scission/bond-forming sequences.

AB - Organolanthanide complexes of the type Cp’2LnR (Cp’ = η5-Me5C5; Ln = La, Nd, Sm, Y, Lu; R = H, CH(SiMe3)2), Me2SiCp″2LnR (Cp″ = η5-Me4C5; Ln = Nd; R = CH(SiMe3)2), Cp’2Sm, and Cp’2Sm(THF)2 catalyze the rapid dehydrogenative oligomerization of PhSiH3. Kinetic and mechanistic arguments exclude the importance of metal-centered redox processes in the catalytic cycle and support instead “four-center” “heterolytic” bond-scission/bond-forming sequences.

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Organolanthanide-Catalyzed Dehydrogenative Coupling of Silanes. Mechanistic Implications

Abstract

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