Reductive Coupling of Carbon Monoxide in a Rhenium Carbonyl Complex with Pendant Lewis Acids
Abstract
Phosphinoborane ligands impart unique reactivity to a rhenium carbonyl cation relative to simple phosphine complexes. Addition of either triethylborohydride or a platinum hydride (that can be formed from H2) forms a rhenium boroxycarbene. This carbene, which crystallizes as a dimer, disproportionates over a period of days to afford the starting cation and a structurally unprecedented boroxy(boroxymethyl)carbene, in which a new C−C bond has been formed between two reduced CO ligands. This product of C−C bond formation can be independently synthesized by addition of 2 equiv of hydride to the rhenium carbonyl cation.
Additional Information
© 2008 American Chemical Society. Received July 2, 2008. Web Release Date: August 15, 2008. Larry Henling and Dr. Michael Day assisted with crystallography. A.J.M.M. is grateful to Dr. Paul R. Elowe for enlightening discussions. This research was generously funded by BP through the Methane Conversion Cooperative (MC^2) program. Supporting Information Available. Full details on synthesis and characterization for compounds 1−5, NMR experiments, and crystallographic information are available. This information is available free of charge via the Internet at http://pubs.acs.org.Attached Files
Supplemental Material - MILjacs08File002.cif
Supplemental Material - MILjacs08File003.cif
Supplemental Material - MILjacs08File004.cif
Supplemental Material - MILjacs08File007.cif
Supplemental Material - MILjacs08supp.pdf
Cover Image - MILjacs08.gif
Files
| Name | Size | Download all |
|---|---|---|
|
md5:0cb9d2c5213b62e046ad6c5d5285fa05
|
2.8 kB | Download |
|
md5:5ad8a52e9f330df985fb3ba00d8971b1
|
2.8 kB | Preview Download |
|
md5:949d17ba25404adaba6b793931eb5a3b
|
2.8 kB | Download |
|
md5:1ce487ba23af23d64a5abb79209836cd
|
4.3 kB | Preview Download |
|
md5:a3fd5bb2863573e78d0422465392363e
|
2.8 kB | Download |
|
md5:197ab09d9237365fbe21c11397452f61
|
13.6 kB | Preview Download |
|
md5:44cec1f9293c8daa8e6fce4051ceee7d
|
25.9 kB | Download |
|
md5:8ecdb690aaf27f72dc0e3aeed3a91bf1
|
2.4 kB | Preview Download |
Additional details
- Eprint ID
- 11804
- DOI
- 10.1021/ja805108z
- Resolver ID
- CaltechAUTHORS:MILjacs08
- BP MC2 program
- Created
-
2008-09-30Created from EPrint's datestamp field
- Updated
-
2021-11-08Created from EPrint's last_modified field