Well-defined silica-supported Mo-alkylidene catalyst precursors containing one OR substituent: Methods of preparation and structure-reactivity relationship in alkene metathesis

Nuria Rendón; Romain Berthoud; Frédéric Blanc; David Gajan; Tarun Maishal; Jean Marie Basset; Christophe Copéret; Anne Lesage; Lyndon Emsley; Smaranda C. Marinescu; Rojendra Singh; Richard R. Schrock

doi:10.1002/chem.200802465

Well-defined silica-supported Mo-alkylidene catalyst precursors containing one OR substituent: Methods of preparation and structure-reactivity relationship in alkene metathesis

Nuria Rendón^*, Romain Berthoud, Frédéric Blanc, David Gajan, Tarun Maishal, Jean Marie Basset, Christophe Copéret, Anne Lesage, Lyndon Emsley, Smaranda C. Marinescu, Rojendra Singh, Richard R. Schrock

^*Corresponding author for this work

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

59 Scopus citations

Abstract

The monosiloxy surface complexes [(≡SiO)Mo(≡NAr)(=CHC-Me ₂R′)(OR)± (R′ = Me or Ph; OR = OtBu, OCMe(CF ₃)₂ or OAr) are obtained by grafting onto SiO _2-(700) either symmetric Mo-alkylidene derivatives [Mo(≡NAr)(=CHCMe₂R′)(OR)₂± or asymmetric derivatives, that is, with two different pendant ligands, one amido and one alkoxy/aryloxy, [Mo(≡ NAr)(=CHCMe₂R′)(OR)(NC ₆H₈)±. The formation of these complexes was confirmed by mass-balance analysis, and infrared (IR) and NMR spectroscopies. These systems are highly efficient catalyst precursors for the metathesis of acyclic alkenes; the best results were seen when OR = OCMe-(CF₃) ₂. Nevertheless, they display poor performances in ring-closing metathesis, possibly due to the rigidity of the metal center (as evidenced by NMR spectroscopy), which therefore slows the rate of the metathesis.

Original language	English (US)
Pages (from-to)	5083-5089
Number of pages	7
Journal	Chemistry - A European Journal
Volume	15
Issue number	20
DOIs	https://doi.org/10.1002/chem.200802465
State	Published - May 11 2009
Externally published	Yes

Keywords

Metathesis
Molybdenum
Silica supports
Solid-state NMR spectroscopy
Surface chemistry

ASJC Scopus subject areas

General Chemistry
Catalysis
Organic Chemistry

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10.1002/chem.200802465

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Rendón, N., Berthoud, R., Blanc, F., Gajan, D., Maishal, T., Basset, J. M., Copéret, C., Lesage, A., Emsley, L., Marinescu, S. C., Singh, R., & Schrock, R. R. (2009). Well-defined silica-supported Mo-alkylidene catalyst precursors containing one OR substituent: Methods of preparation and structure-reactivity relationship in alkene metathesis. Chemistry - A European Journal, 15(20), 5083-5089. https://doi.org/10.1002/chem.200802465

@article{cca8913956bd4100b47e30e1694dc542,

title = "Well-defined silica-supported Mo-alkylidene catalyst precursors containing one OR substituent: Methods of preparation and structure-reactivity relationship in alkene metathesis",

abstract = "The monosiloxy surface complexes [(≡SiO)Mo(≡NAr)(=CHC-Me 2R′)(OR)± (R′ = Me or Ph; OR = OtBu, OCMe(CF 3)2 or OAr) are obtained by grafting onto SiO 2-(700) either symmetric Mo-alkylidene derivatives [Mo(≡NAr)(=CHCMe2R′)(OR)2± or asymmetric derivatives, that is, with two different pendant ligands, one amido and one alkoxy/aryloxy, [Mo(≡ NAr)(=CHCMe2R′)(OR)(NC 6H8)±. The formation of these complexes was confirmed by mass-balance analysis, and infrared (IR) and NMR spectroscopies. These systems are highly efficient catalyst precursors for the metathesis of acyclic alkenes; the best results were seen when OR = OCMe-(CF3) 2. Nevertheless, they display poor performances in ring-closing metathesis, possibly due to the rigidity of the metal center (as evidenced by NMR spectroscopy), which therefore slows the rate of the metathesis.",

keywords = "Metathesis, Molybdenum, Silica supports, Solid-state NMR spectroscopy, Surface chemistry",

author = "Nuria Rend{\'o}n and Romain Berthoud and Fr{\'e}d{\'e}ric Blanc and David Gajan and Tarun Maishal and Basset, {Jean Marie} and Christophe Cop{\'e}ret and Anne Lesage and Lyndon Emsley and Marinescu, {Smaranda C.} and Rojendra Singh and Schrock, {Richard R.}",

year = "2009",

month = may,

day = "11",

doi = "10.1002/chem.200802465",

language = "English (US)",

volume = "15",

pages = "5083--5089",

journal = "Chemistry - A European Journal",

issn = "0947-6539",

publisher = "Wiley-VCH Verlag",

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Rendón, N, Berthoud, R, Blanc, F, Gajan, D, Maishal, T, Basset, JM, Copéret, C, Lesage, A, Emsley, L, Marinescu, SC, Singh, R & Schrock, RR 2009, 'Well-defined silica-supported Mo-alkylidene catalyst precursors containing one OR substituent: Methods of preparation and structure-reactivity relationship in alkene metathesis', Chemistry - A European Journal, vol. 15, no. 20, pp. 5083-5089. https://doi.org/10.1002/chem.200802465

Well-defined silica-supported Mo-alkylidene catalyst precursors containing one OR substituent: Methods of preparation and structure-reactivity relationship in alkene metathesis. / Rendón, Nuria; Berthoud, Romain; Blanc, Frédéric et al.
In: Chemistry - A European Journal, Vol. 15, No. 20, 11.05.2009, p. 5083-5089.

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

TY - JOUR

T1 - Well-defined silica-supported Mo-alkylidene catalyst precursors containing one OR substituent

T2 - Methods of preparation and structure-reactivity relationship in alkene metathesis

AU - Rendón, Nuria

AU - Berthoud, Romain

AU - Blanc, Frédéric

AU - Gajan, David

AU - Maishal, Tarun

AU - Basset, Jean Marie

AU - Copéret, Christophe

AU - Lesage, Anne

AU - Emsley, Lyndon

AU - Marinescu, Smaranda C.

AU - Singh, Rojendra

AU - Schrock, Richard R.

PY - 2009/5/11

Y1 - 2009/5/11

N2 - The monosiloxy surface complexes [(≡SiO)Mo(≡NAr)(=CHC-Me 2R′)(OR)± (R′ = Me or Ph; OR = OtBu, OCMe(CF 3)2 or OAr) are obtained by grafting onto SiO 2-(700) either symmetric Mo-alkylidene derivatives [Mo(≡NAr)(=CHCMe2R′)(OR)2± or asymmetric derivatives, that is, with two different pendant ligands, one amido and one alkoxy/aryloxy, [Mo(≡ NAr)(=CHCMe2R′)(OR)(NC 6H8)±. The formation of these complexes was confirmed by mass-balance analysis, and infrared (IR) and NMR spectroscopies. These systems are highly efficient catalyst precursors for the metathesis of acyclic alkenes; the best results were seen when OR = OCMe-(CF3) 2. Nevertheless, they display poor performances in ring-closing metathesis, possibly due to the rigidity of the metal center (as evidenced by NMR spectroscopy), which therefore slows the rate of the metathesis.

AB - The monosiloxy surface complexes [(≡SiO)Mo(≡NAr)(=CHC-Me 2R′)(OR)± (R′ = Me or Ph; OR = OtBu, OCMe(CF 3)2 or OAr) are obtained by grafting onto SiO 2-(700) either symmetric Mo-alkylidene derivatives [Mo(≡NAr)(=CHCMe2R′)(OR)2± or asymmetric derivatives, that is, with two different pendant ligands, one amido and one alkoxy/aryloxy, [Mo(≡ NAr)(=CHCMe2R′)(OR)(NC 6H8)±. The formation of these complexes was confirmed by mass-balance analysis, and infrared (IR) and NMR spectroscopies. These systems are highly efficient catalyst precursors for the metathesis of acyclic alkenes; the best results were seen when OR = OCMe-(CF3) 2. Nevertheless, they display poor performances in ring-closing metathesis, possibly due to the rigidity of the metal center (as evidenced by NMR spectroscopy), which therefore slows the rate of the metathesis.

KW - Metathesis

KW - Molybdenum

KW - Silica supports

KW - Solid-state NMR spectroscopy

KW - Surface chemistry

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U2 - 10.1002/chem.200802465

DO - 10.1002/chem.200802465

M3 - Article

C2 - 19343757

AN - SCOPUS:66149144329

SN - 0947-6539

VL - 15

SP - 5083

EP - 5089

JO - Chemistry - A European Journal

JF - Chemistry - A European Journal

IS - 20

ER -

Well-defined silica-supported Mo-alkylidene catalyst precursors containing one OR substituent: Methods of preparation and structure-reactivity relationship in alkene metathesis

Abstract

Keywords

ASJC Scopus subject areas

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