Oxy-functionalization of nucleophilic rhenium(I) metal carbon bonds catalyzed by selenium(IV)

William J. Tenn; Brian L. Conley; Claas H. Hövelmann; Märten Ahlquist; Robert J. Nielsen; Daniel H. Ess; Jonas Oxgaard; Steven M. Bischof; William A. Goddard; Roy A. Periana

doi:10.1021/ja806814c

Oxy-functionalization of nucleophilic rhenium(I) metal carbon bonds catalyzed by selenium(IV)

William J. Tenn
, Brian L. Conley
, Claas H. Hövelmann
, Märten Ahlquist
, Robert J. Nielsen
, Daniel H. Ess
, Jonas Oxgaard
, Steven M. Bischof
, William A. Goddard
, Roy A. Periana

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

Abstract

We report that SeO ₂ catalyzes the facile oxy-functionalization of (CO) ₅Re(I)-Me ₄- with IO ₄- to generate methanol. Mechanistic studies and DFT calculations reveal that catalysis involves methyl group transfer from Re to the electrophilic Se center followed by oxidation and subsequent reductive functionalization of the resulting CH3Se(VI) species. Furthermore, (CO) ₃Re(I)(Bpy)-R (R = ethyl, n-propyl, and aryl) complexes show analogous transfer to SeO ₂ to generate the primary alcohols. This represents a new strategy for the oxy-functionalization of M-R4- polarized bonds.

Original language	English
Pages (from-to)	2466-2468
Number of pages	3
Journal	Journal of the American Chemical Society
Volume	131
Issue number	7
DOIs	https://doi.org/10.1021/ja806814c
Publication status	Published - 25 Feb 2009
Externally published	Yes

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@article{492a68b7fe564e39b2acb404d6515547,

title = "Oxy-functionalization of nucleophilic rhenium(I) metal carbon bonds catalyzed by selenium(IV)",

abstract = "We report that SeO 2 catalyzes the facile oxy-functionalization of (CO) 5Re(I)-Me 4- with IO 4- to generate methanol. Mechanistic studies and DFT calculations reveal that catalysis involves methyl group transfer from Re to the electrophilic Se center followed by oxidation and subsequent reductive functionalization of the resulting CH3Se(VI) species. Furthermore, (CO) 3Re(I)(Bpy)-R (R = ethyl, n-propyl, and aryl) complexes show analogous transfer to SeO 2 to generate the primary alcohols. This represents a new strategy for the oxy-functionalization of M-R4- polarized bonds.",

author = "Tenn, \{William J.\} and Conley, \{Brian L.\} and H{\"o}velmann, \{Claas H.\} and M{\"a}rten Ahlquist and Nielsen, \{Robert J.\} and Ess, \{Daniel H.\} and Jonas Oxgaard and Bischof, \{Steven M.\} and Goddard, \{William A.\} and Periana, \{Roy A.\}",

year = "2009",

month = feb,

day = "25",

doi = "10.1021/ja806814c",

language = "English",

volume = "131",

pages = "2466--2468",

journal = "Journal of the American Chemical Society",

issn = "0002-7863",

number = "7",

}

TY - JOUR

T1 - Oxy-functionalization of nucleophilic rhenium(I) metal carbon bonds catalyzed by selenium(IV)

AU - Tenn, William J.

AU - Conley, Brian L.

AU - Hövelmann, Claas H.

AU - Ahlquist, Märten

AU - Nielsen, Robert J.

AU - Ess, Daniel H.

AU - Oxgaard, Jonas

AU - Bischof, Steven M.

AU - Goddard, William A.

AU - Periana, Roy A.

PY - 2009/2/25

Y1 - 2009/2/25

N2 - We report that SeO 2 catalyzes the facile oxy-functionalization of (CO) 5Re(I)-Me 4- with IO 4- to generate methanol. Mechanistic studies and DFT calculations reveal that catalysis involves methyl group transfer from Re to the electrophilic Se center followed by oxidation and subsequent reductive functionalization of the resulting CH3Se(VI) species. Furthermore, (CO) 3Re(I)(Bpy)-R (R = ethyl, n-propyl, and aryl) complexes show analogous transfer to SeO 2 to generate the primary alcohols. This represents a new strategy for the oxy-functionalization of M-R4- polarized bonds.

AB - We report that SeO 2 catalyzes the facile oxy-functionalization of (CO) 5Re(I)-Me 4- with IO 4- to generate methanol. Mechanistic studies and DFT calculations reveal that catalysis involves methyl group transfer from Re to the electrophilic Se center followed by oxidation and subsequent reductive functionalization of the resulting CH3Se(VI) species. Furthermore, (CO) 3Re(I)(Bpy)-R (R = ethyl, n-propyl, and aryl) complexes show analogous transfer to SeO 2 to generate the primary alcohols. This represents a new strategy for the oxy-functionalization of M-R4- polarized bonds.

UR - https://www.scopus.com/pages/publications/67849090939

U2 - 10.1021/ja806814c

DO - 10.1021/ja806814c

M3 - Article

AN - SCOPUS:67849090939

SN - 0002-7863

VL - 131

SP - 2466

EP - 2468

JO - Journal of the American Chemical Society

JF - Journal of the American Chemical Society

IS - 7

ER -

Oxy-functionalization of nucleophilic rhenium(I) metal carbon bonds catalyzed by selenium(IV)

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