Reactions of Titanocene Bis(trimethylsilyl)acetylene Complexes with Carbodiimides: An Experimental and Theoretical Study of Complexation versus C-N Bond Activation
Data(s) |
2012
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Resumo |
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. |
Formato |
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Identificador |
http://eprints.iisc.ernet.in/45499/1/jol_AMC_134-38_15979_2012.pdf http://eprints.iisc.ernet.in/45499/8/ja3070649_si_007.pdf http://eprints.iisc.ernet.in/45499/17/ja3070649_si_001.cif http://eprints.iisc.ernet.in/45499/18/ja3070649_si_002.cif http://eprints.iisc.ernet.in/45499/19/ja3070649_si_003.cif http://eprints.iisc.ernet.in/45499/20/ja3070649_si_004.cif http://eprints.iisc.ernet.in/45499/21/ja3070649_si_005.cif http://eprints.iisc.ernet.in/45499/22/ja3070649_si_006.cif 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. |
Publicador |
American Chemical Society |
Relação |
http://dx.doi.org/10.1021/ja3070649 http://eprints.iisc.ernet.in/45499/ |
Palavras-Chave | #Inorganic & Physical Chemistry |
Tipo |
Journal Article PeerReviewed |