Organoactinides - Novel catalysts for demanding chemical transformations

Aswini K. Dash; Ylia Gurevizt; Ji Quan Wang; Jiaxi Wang; Moshe Kapon; Moris S. Eisen

doi:10.1016/S0925-8388(02)00307-9

Organoactinides - Novel catalysts for demanding chemical transformations

Aswini K. Dash, Ylia Gurevizt, Ji Quan Wang, Jiaxi Wang, Moshe Kapon, Moris S. Eisen^*

^*Corresponding author for this work

Research output: Contribution to journal › Conference article › peer-review

8 Scopus citations

Abstract

The catalytic effect obtained by opening the coordination sphere of the organoactinide complex is presented. Replacing the pentamethylcyclopentadienyl ligand in Cp*₂ThCl₂ (Cp* = C₅Me₅) by the bridge ligation [Me₂SiCp₂″]^2- 2[Li]⁺ (Cp″ = C₅Me₄) affords the synthesis of ansa-Me₂SiCp₂″ThCl₂, which reacts with two equiv of BuLi affording the corresponding dibutyl complex ansa-Me₂SiCp₂″Th″Bu₂. This latter complex was found to be an active catalyst for the dimerization of terminal alkynes, and in the hydrosilylation of terminal alkynes with PhSiH₃. In both processes a large chemoselectivity and regioselectivity are achieved due to the hindered equatorial plane, attributed to the disposition of the methyl groups in the bridge ligation, forcing the incoming substrates to react with a specific regiochemistry.

Original language	English
Pages (from-to)	65-69
Number of pages	5
Journal	Journal of Alloys and Compounds
Volume	344
Issue number	1-2
DOIs	https://doi.org/10.1016/S0925-8388(02)00307-9
State	Published - 7 Oct 2002
Externally published	Yes
Event	Rare Earths 2001 - Sao Paulo, Brazil Duration: 7 Oct 2002 → 7 Oct 2002

Keywords

Alkynes
Catalysis
Dimerization
Hydrosilylation
Organoactinides
Organometall ic complexes

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10.1016/S0925-8388(02)00307-9

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title = "Organoactinides - Novel catalysts for demanding chemical transformations",

abstract = "The catalytic effect obtained by opening the coordination sphere of the organoactinide complex is presented. Replacing the pentamethylcyclopentadienyl ligand in Cp*2ThCl2 (Cp* = C5Me5) by the bridge ligation [Me2SiCp2″]2- 2[Li]+ (Cp″ = C5Me4) affords the synthesis of ansa-Me2SiCp2″ThCl2, which reacts with two equiv of BuLi affording the corresponding dibutyl complex ansa-Me2SiCp2″Th″Bu2. This latter complex was found to be an active catalyst for the dimerization of terminal alkynes, and in the hydrosilylation of terminal alkynes with PhSiH3. In both processes a large chemoselectivity and regioselectivity are achieved due to the hindered equatorial plane, attributed to the disposition of the methyl groups in the bridge ligation, forcing the incoming substrates to react with a specific regiochemistry.",

keywords = "Alkynes, Catalysis, Dimerization, Hydrosilylation, Organoactinides, Organometall ic complexes",

author = "Dash, {Aswini K.} and Ylia Gurevizt and Wang, {Ji Quan} and Jiaxi Wang and Moshe Kapon and Eisen, {Moris S.}",

note = "Funding Information: This research was supported by The Israel Science Foundation, administered by The Israel Academy of Sciences and Humanities under contract 83/01-1; by the Henri Gutwirth Fund for the Promotion of Research at the Technion and by the E. and J. Bishop Research Fund. A.K.D. thanks the Technion for a postdoctoral fellowship.; Rare Earths 2001 ; Conference date: 07-10-2002 Through 07-10-2002",

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AU - Dash, Aswini K.

AU - Gurevizt, Ylia

AU - Wang, Ji Quan

AU - Wang, Jiaxi

AU - Kapon, Moshe

AU - Eisen, Moris S.

N1 - Funding Information: This research was supported by The Israel Science Foundation, administered by The Israel Academy of Sciences and Humanities under contract 83/01-1; by the Henri Gutwirth Fund for the Promotion of Research at the Technion and by the E. and J. Bishop Research Fund. A.K.D. thanks the Technion for a postdoctoral fellowship.

PY - 2002/10/7

Y1 - 2002/10/7

N2 - The catalytic effect obtained by opening the coordination sphere of the organoactinide complex is presented. Replacing the pentamethylcyclopentadienyl ligand in Cp*2ThCl2 (Cp* = C5Me5) by the bridge ligation [Me2SiCp2″]2- 2[Li]+ (Cp″ = C5Me4) affords the synthesis of ansa-Me2SiCp2″ThCl2, which reacts with two equiv of BuLi affording the corresponding dibutyl complex ansa-Me2SiCp2″Th″Bu2. This latter complex was found to be an active catalyst for the dimerization of terminal alkynes, and in the hydrosilylation of terminal alkynes with PhSiH3. In both processes a large chemoselectivity and regioselectivity are achieved due to the hindered equatorial plane, attributed to the disposition of the methyl groups in the bridge ligation, forcing the incoming substrates to react with a specific regiochemistry.

AB - The catalytic effect obtained by opening the coordination sphere of the organoactinide complex is presented. Replacing the pentamethylcyclopentadienyl ligand in Cp*2ThCl2 (Cp* = C5Me5) by the bridge ligation [Me2SiCp2″]2- 2[Li]+ (Cp″ = C5Me4) affords the synthesis of ansa-Me2SiCp2″ThCl2, which reacts with two equiv of BuLi affording the corresponding dibutyl complex ansa-Me2SiCp2″Th″Bu2. This latter complex was found to be an active catalyst for the dimerization of terminal alkynes, and in the hydrosilylation of terminal alkynes with PhSiH3. In both processes a large chemoselectivity and regioselectivity are achieved due to the hindered equatorial plane, attributed to the disposition of the methyl groups in the bridge ligation, forcing the incoming substrates to react with a specific regiochemistry.

KW - Alkynes

KW - Catalysis

KW - Dimerization

KW - Hydrosilylation

KW - Organoactinides

KW - Organometall ic complexes

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U2 - 10.1016/S0925-8388(02)00307-9

DO - 10.1016/S0925-8388(02)00307-9

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SN - 0925-8388

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JO - Journal of Alloys and Compounds

JF - Journal of Alloys and Compounds

IS - 1-2

T2 - Rare Earths 2001

Y2 - 7 October 2002 through 7 October 2002

ER -

Organoactinides - Novel catalysts for demanding chemical transformations

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