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Reactions of Titanocene Bis(trimethylsilyl)acetylene Complexes with Carbodiimides: An Experimental and Theoretical Study of Complexation versus C-N Bond Activation

Haehnel, Martin and Ruhmann, Martin and Theilmann, Oliver and Roy, Subhendu and Beweries, Torsten and Arndt, Perdita and Spannenberg, Anke and Villinger, Alexander and Jemmis, Eluvathingal D and Schulz, Axel and Rosenthal, Uwe (2012) Reactions of Titanocene Bis(trimethylsilyl)acetylene Complexes with Carbodiimides: An Experimental and Theoretical Study of Complexation versus C-N Bond Activation. In: JOURNAL OF THE AMERICAN CHEMICAL SOCIETY, 134 (38). pp. 15979-15991.

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Official URL: http://dx.doi.org/10.1021/ja3070649

Abstract

The reaction of the low valent metallocene(II) sources Cp'Ti-2(eta(2)-Me3SiC2SiMe3) (Cp' = eta(5)-cyclopentadienyl, 1a or eta(5)-pentamethylcyclopentadienyl, 1b) with different carbodiimide substrates RN=C=NR' 2-R-R' (R = t-Bu; R' = Et; R = R' = i-Pr; t-Bu; SiMe3; 2,4,6-Me-C6H2 and 2,6-i-Pr-C6H3) was investigated to explore the frontiers of ring strained, unusual four-membered heterometallacycles 5-R. The product complexes show dismantlement, isomerization, or C-C coupling of the applied carbodiimide substrates, respectively, to form unusual mono-, di-, and tetranuclear titanium(III) complexes. A detailed theoretical study revealed that the formation of the unusual complexes can be attributed to the biradicaloid nature of the unusual four-membered heterometallacycles 5-R, which presents an intriguing situation of M-C bonding. The combined experimental and theoretical study highlights the delicate interplay of electronic and steric effects in the stabilization of strained four-membered heterometallacycles, accounting for the isolation of the obtained complexes.

Item Type: Journal Article
Additional Information: Copyright for this article belongs to American Chemical Society, WASHINGTON
Department/Centre: Division of Chemical Sciences > Inorganic & Physical Chemistry
Depositing User: Francis Jayakanth
Date Deposited: 13 Dec 2012 05:21
Last Modified: 13 Dec 2012 05:24
URI: http://eprints.iisc.ac.in/id/eprint/45499

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