Silylation of Iron-Bound Carbon Monoxide Affords a Terminal Fe Carbyne

Cited 68 time in webofscience Cited 0 time in scopus
  • Hit : 483
  • Download : 0
A series of monocarbonyl iron complexes in the formal oxidation states 0, +1, and +2 are accessible when supported by a tetradentate tris(phosphino)silyl ligand (SiPiPr 3 = [Si(o-C(6)H(4)PiPr(2))(3)](-)). X-ray diffraction (XRD) studies of these carbonyl complexes establish little geometrical change about the iron center as a function of oxidation state. It is possible to functionalize the terminal CO ligand of the most reduced carbonyl adduct by addition of SiMe3+ to afford a well-defined iron carbyne species, (SiP3iPr)Fe equivalent to C-OSiMe3. Single-crystal XRD data of this iron carbyne derivative reveal an unusually short Fe equivalent to C-OSiMe3 bond distance (1.671(2) angstrom) and a substantially elongated C-O distance (1.278(3) angstrom), consistent with Fe-C carbyne character. The overall trigonal bipyramidal geometry of (SiP3iPr)Fe equivalent to C-OSiMe3 compares well with that of the corresponding carbonyls, (SiP3iPr)Fe(CO)(-), (SiP3iPr)Fe(CO), and (SiP3iPr)Fe(CO)(+). Details regarding the electronic structure of the carbyne complex have been explored via the collection of comparative Mossbauer data for all of the complexes featured and also via DFT calculations. In sum, these data point to a strongly a-accepting Fischer-type carbyne ligand that confers stability to a low-valent iron(0) rather than high-valent iron(IV) center.
Publisher
AMER CHEMICAL SOC
Issue Date
2011-03
Language
English
Article Type
Article
Keywords

MOLECULAR-STRUCTURE; TRIS(PHOSPHINO)SILYL LIGANDS; ORGANOMETALLIC COMPLEXES; MOSSBAUER PARAMETERS; REDUCTIVE CLEAVAGE; CRYSTAL-STRUCTURE; MONOVALENT IRON; IMIDO COMPLEX; METAL; REACTIVITY

Citation

JOURNAL OF THE AMERICAN CHEMICAL SOCIETY, v.133, no.12, pp.4438 - 4446

ISSN
0002-7863
DOI
10.1021/ja109678y
URI
http://hdl.handle.net/10203/97760
Appears in Collection
CH-Journal Papers(저널논문)
Files in This Item
There are no files associated with this item.
This item is cited by other documents in WoS
⊙ Detail Information in WoSⓡ Click to see webofscience_button
⊙ Cited 68 items in WoS Click to see citing articles in records_button

qr_code

  • mendeley

    citeulike


rss_1.0 rss_2.0 atom_1.0