Controlling the hydrogenolysis of silica-supported tungsten pentamethyl leads to a class of highly electron deficient partially alkylated metal hydrides

Niladri Maity; Samir Barman; Emmanuel Callens; Manoja K. Samantaray; Edy Abou-Hamad; Yury Minenkov; Valerio D'Elia; Adam S. Hoffman; Cory M. Widdifield; Luigi Cavallo; Bruce C. Gates; Jean Marie Basset

doi:10.1039/c5sc03490f

Controlling the hydrogenolysis of silica-supported tungsten pentamethyl leads to a class of highly electron deficient partially alkylated metal hydrides

Niladri Maity, Samir Barman, Emmanuel Callens^*, Manoja K. Samantaray, Edy Abou-Hamad, Yury Minenkov, Valerio D'Elia, Adam S. Hoffman, Cory M. Widdifield, Luigi Cavallo, Bruce C. Gates, Jean Marie Basset

^*Corresponding author for this work

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

51 Scopus citations

Abstract

The well-defined single-site silica-supported tungsten complex [(Si-O-)W(Me)₅], 1, is an excellent precatalyst for alkane metathesis. The unique structure of 1 allows the synthesis of unprecedented tungsten hydrido methyl surface complexes via a controlled hydrogenolysis. Specifically, in the presence of molecular hydrogen, 1 is quickly transformed at -78 °C into a partially alkylated tungsten hydride, 4, as characterized by ¹H solid-state NMR and IR spectroscopies. Species 4, upon warming to 150 °C, displays the highest catalytic activity for propane metathesis yet reported. DFT calculations using model systems support the formation of [(Si-O-)WH₃(Me)₂], as the predominant species at -78 °C following several elementary steps of hydrogen addition (by σ-bond metathesis or α-hydrogen transfer). Rearrangement of 4 occuring between -78 °C and room temperature leads to the formation of an unique methylidene tungsten hydride [(Si-O-)WH₃(CH₂)], as determined by solid-state ¹H and ¹³C NMR spectroscopies and supported by DFT. Thus for the first time, a coordination sphere that incorporates both carbene and hydride functionalities has been observed.

Original language	English
Pages (from-to)	1558-1568
Number of pages	11
Journal	Chemical Science
Volume	7
Issue number	2
DOIs	https://doi.org/10.1039/c5sc03490f
State	Published - 2016
Externally published	Yes

Bibliographical note

Funding Information:
The research was supported by the King Abdullah University of Science and Technology. The authors acknowledge Prof. Lyndon Emsley and Dr Aaron J. Rossini (EPFL) for their assistance. The work at the University of California was supported by the U.S. Department of Energy (DOE), Office of Science, Basic Energy Sciences, Grant DE-FG02-04ER15513. We acknowledge beam time at beamline 4-1 at the Stanford Synchrotron Radiation Lightsource supported by the DOE Division of Materials Sciences. We thank the beam line staff for valuable support. C. M. W. acknowledges the Natural Sciences and Engineering Council of Canada (NSERC) for a postdoctoral fellowship. Computational resources for selected DFT calculations were provided by the P?ole Scienti?que de Mod?elisation Num?erique (PSMN).

Publisher Copyright:
© 2016 The Royal Society of Chemistry.

ASJC Scopus subject areas

General Chemistry

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10.1039/c5sc03490f

Cite this

Maity, N., Barman, S., Callens, E., Samantaray, M. K., Abou-Hamad, E., Minenkov, Y., D'Elia, V., Hoffman, A. S., Widdifield, C. M., Cavallo, L., Gates, B. C., & Basset, J. M. (2016). Controlling the hydrogenolysis of silica-supported tungsten pentamethyl leads to a class of highly electron deficient partially alkylated metal hydrides. Chemical Science, 7(2), 1558-1568. https://doi.org/10.1039/c5sc03490f

@article{087221c45bd1423082c2c1e4adbab36d,

title = "Controlling the hydrogenolysis of silica-supported tungsten pentamethyl leads to a class of highly electron deficient partially alkylated metal hydrides",

abstract = "The well-defined single-site silica-supported tungsten complex [(Si-O-)W(Me)5], 1, is an excellent precatalyst for alkane metathesis. The unique structure of 1 allows the synthesis of unprecedented tungsten hydrido methyl surface complexes via a controlled hydrogenolysis. Specifically, in the presence of molecular hydrogen, 1 is quickly transformed at -78 °C into a partially alkylated tungsten hydride, 4, as characterized by 1H solid-state NMR and IR spectroscopies. Species 4, upon warming to 150 °C, displays the highest catalytic activity for propane metathesis yet reported. DFT calculations using model systems support the formation of [(Si-O-)WH3(Me)2], as the predominant species at -78 °C following several elementary steps of hydrogen addition (by σ-bond metathesis or α-hydrogen transfer). Rearrangement of 4 occuring between -78 °C and room temperature leads to the formation of an unique methylidene tungsten hydride [(Si-O-)WH3(CH2)], as determined by solid-state 1H and 13C NMR spectroscopies and supported by DFT. Thus for the first time, a coordination sphere that incorporates both carbene and hydride functionalities has been observed.",

author = "Niladri Maity and Samir Barman and Emmanuel Callens and Samantaray, \{Manoja K.\} and Edy Abou-Hamad and Yury Minenkov and Valerio D'Elia and Hoffman, \{Adam S.\} and Widdifield, \{Cory M.\} and Luigi Cavallo and Gates, \{Bruce C.\} and Basset, \{Jean Marie\}",

note = "Funding Information: The research was supported by the King Abdullah University of Science and Technology. The authors acknowledge Prof. Lyndon Emsley and Dr Aaron J. Rossini (EPFL) for their assistance. The work at the University of California was supported by the U.S. Department of Energy (DOE), Office of Science, Basic Energy Sciences, Grant DE-FG02-04ER15513. We acknowledge beam time at beamline 4-1 at the Stanford Synchrotron Radiation Lightsource supported by the DOE Division of Materials Sciences. We thank the beam line staff for valuable support. C. M. W. acknowledges the Natural Sciences and Engineering Council of Canada (NSERC) for a postdoctoral fellowship. Computational resources for selected DFT calculations were provided by the P?ole Scienti?que de Mod?elisation Num?erique (PSMN). Publisher Copyright: {\textcopyright} 2016 The Royal Society of Chemistry.",

year = "2016",

doi = "10.1039/c5sc03490f",

language = "English",

volume = "7",

pages = "1558--1568",

journal = "Chemical Science",

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Maity, N, Barman, S, Callens, E, Samantaray, MK, Abou-Hamad, E, Minenkov, Y, D'Elia, V, Hoffman, AS, Widdifield, CM, Cavallo, L, Gates, BC & Basset, JM 2016, 'Controlling the hydrogenolysis of silica-supported tungsten pentamethyl leads to a class of highly electron deficient partially alkylated metal hydrides', Chemical Science, vol. 7, no. 2, pp. 1558-1568. https://doi.org/10.1039/c5sc03490f

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T1 - Controlling the hydrogenolysis of silica-supported tungsten pentamethyl leads to a class of highly electron deficient partially alkylated metal hydrides

AU - Maity, Niladri

AU - Barman, Samir

AU - Callens, Emmanuel

AU - Samantaray, Manoja K.

AU - Abou-Hamad, Edy

AU - Minenkov, Yury

AU - D'Elia, Valerio

AU - Hoffman, Adam S.

AU - Widdifield, Cory M.

AU - Cavallo, Luigi

AU - Gates, Bruce C.

AU - Basset, Jean Marie

N1 - Funding Information: The research was supported by the King Abdullah University of Science and Technology. The authors acknowledge Prof. Lyndon Emsley and Dr Aaron J. Rossini (EPFL) for their assistance. The work at the University of California was supported by the U.S. Department of Energy (DOE), Office of Science, Basic Energy Sciences, Grant DE-FG02-04ER15513. We acknowledge beam time at beamline 4-1 at the Stanford Synchrotron Radiation Lightsource supported by the DOE Division of Materials Sciences. We thank the beam line staff for valuable support. C. M. W. acknowledges the Natural Sciences and Engineering Council of Canada (NSERC) for a postdoctoral fellowship. Computational resources for selected DFT calculations were provided by the P?ole Scienti?que de Mod?elisation Num?erique (PSMN). Publisher Copyright: © 2016 The Royal Society of Chemistry.

PY - 2016

Y1 - 2016

N2 - The well-defined single-site silica-supported tungsten complex [(Si-O-)W(Me)5], 1, is an excellent precatalyst for alkane metathesis. The unique structure of 1 allows the synthesis of unprecedented tungsten hydrido methyl surface complexes via a controlled hydrogenolysis. Specifically, in the presence of molecular hydrogen, 1 is quickly transformed at -78 °C into a partially alkylated tungsten hydride, 4, as characterized by 1H solid-state NMR and IR spectroscopies. Species 4, upon warming to 150 °C, displays the highest catalytic activity for propane metathesis yet reported. DFT calculations using model systems support the formation of [(Si-O-)WH3(Me)2], as the predominant species at -78 °C following several elementary steps of hydrogen addition (by σ-bond metathesis or α-hydrogen transfer). Rearrangement of 4 occuring between -78 °C and room temperature leads to the formation of an unique methylidene tungsten hydride [(Si-O-)WH3(CH2)], as determined by solid-state 1H and 13C NMR spectroscopies and supported by DFT. Thus for the first time, a coordination sphere that incorporates both carbene and hydride functionalities has been observed.

AB - The well-defined single-site silica-supported tungsten complex [(Si-O-)W(Me)5], 1, is an excellent precatalyst for alkane metathesis. The unique structure of 1 allows the synthesis of unprecedented tungsten hydrido methyl surface complexes via a controlled hydrogenolysis. Specifically, in the presence of molecular hydrogen, 1 is quickly transformed at -78 °C into a partially alkylated tungsten hydride, 4, as characterized by 1H solid-state NMR and IR spectroscopies. Species 4, upon warming to 150 °C, displays the highest catalytic activity for propane metathesis yet reported. DFT calculations using model systems support the formation of [(Si-O-)WH3(Me)2], as the predominant species at -78 °C following several elementary steps of hydrogen addition (by σ-bond metathesis or α-hydrogen transfer). Rearrangement of 4 occuring between -78 °C and room temperature leads to the formation of an unique methylidene tungsten hydride [(Si-O-)WH3(CH2)], as determined by solid-state 1H and 13C NMR spectroscopies and supported by DFT. Thus for the first time, a coordination sphere that incorporates both carbene and hydride functionalities has been observed.

UR - https://www.scopus.com/pages/publications/84961356590

U2 - 10.1039/c5sc03490f

DO - 10.1039/c5sc03490f

M3 - Article

AN - SCOPUS:84961356590

SN - 2041-6520

VL - 7

SP - 1558

EP - 1568

JO - Chemical Science

JF - Chemical Science

IS - 2

ER -

Controlling the hydrogenolysis of silica-supported tungsten pentamethyl leads to a class of highly electron deficient partially alkylated metal hydrides

Abstract

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