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619476 
Journal Article 
Interplay among Tetrahedrane, Butterfly Diradical, and Planar Rhombus Structures in the Chemistry of the Binuclear Iron Carbonyl Phosphi nidene Complexes Fe2(CO)6(PX)2 
Silaghi-Dumitrescu, I; Bitterwolf, TE; King, AB 
2008 
Yes 
Journal of the American Chemical Society
ISSN: 0002-7863
EISSN: 1520-5126 
130 
3 
901-906 
Density functional theory studies on a series of Fe2(CO)6(PX)2 derivatives show the tetrahedrane to be the most stable for the alkyl (X = Me, tBu), P-H (X = H), and chloro (X = Cl) derivatives. However, butterfly diradical and planar rhombus structures are found to be more stable than tetrahedranes for the amino (X = NH2, NMe2, and NiPr2) and aryloxy (R = 2,6-tBu2-4-Me-C6H2O) derivatives. For the chloro (X = Cl) and methoxy (X = OMe) derivatives energetically accessible bishomotetrahedrane Fe2(CO)6P2(u- X)2 isomers are observed in which the X substituents on the phosphorus atoms interact with the iron atom to form two direct Fe-X bonds at the expense of two of the four Fe-P bonds. In addition, the global minimum for the hydroxy (X = OH) derivative is an unusual FeP-butterfly structure with a central Fe-P bond as well as two external Fe-P bonds, one external P-P bond, and one external Fe=Fe double bond. Comparison of calbulated with experimental v(CO) frequencies shows that low-temperature Nujol matrix photolysis of (iPr2NP)2COFe2(CO)6 leads to a planar rhombus rather than a tetrahedrane isomer of Fe2-(CO)6(PNiPr2)2. [ABSTRACT FROM AUTHOR] Copyright of Journal of the American Chemical Society is the property of American Chemical Society and its content may not be copied or emailed to multiple sites or posted to a listserv without the copyright holder's express written permission. However, users may print, download, or email articles for individual use. This abstract may be abridged. No warranty is given about the accuracy of the copy. Users should refer to the original published version of the material for the full abstract. (Copyright applies to all Abstracts) 
CHEMISTRY, Physical & theoretical; DENSITY functionals; PHOSPHORUS; IRON; BONDS