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Issue 7, 2002
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“Bidentate” and “tridentate” sulfonamide ligands for titanium complexes: crystal structures and solution dynamics elucidating an η2 or η3-coordination mode

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Abstract

Highly air- and moisture-sensitive complexes having sulfonamide ligands, (TsNR)2Ti(NMe2)2 (Ts = p-MeC6H4SO2), were prepared by treatment of two equivalents of TsNHR with Ti(NMe2)4 at room temperature. One of the compounds, where R = i-Pr (1), was studied in detail; the crystal structure of 1 revealed that both of the TsNi-Pr ligands were bound to the metal in an η2-coordination mode. Solution dynamics of 1 showed that an η12 interconversion occurred above 60 °C with an activation energy of 15.8 kcal mol−1. Treatment of Ti(NMe2)4 with the sulfonamide TsHN(CH2)2O(CH2)2NHTs (3), led to the formation of [TsN(CH2)2O(CH2)2NTs]Ti(NMe2)2 (2) in high yield, in which the sulfonamide moiety was coordinated to the titanium center in an η3 (NON) mode. No sign of η12 interconversion of the sulfonamide ligands was seen in solution. Treatment of 2 with Me3SiCl resulted in the formation of [{TsN(CH2)2O(CH2)2NTs}Ti(NMe2)Cl]2 (4) and [{TsN(CH2)2O(CH2)2NTs}TiCl2]2 (5). An X-ray structure determination of 4 revealed that sulfonyl oxygen bridging resulted in the formation of an eight membered ring.

Graphical abstract: “Bidentate” and “tridentate” sulfonamide ligands for titanium complexes: crystal structures and solution dynamics elucidating an η2 or η3-coordination mode

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Publication details

The article was received on 15 Nov 2001, accepted on 06 Feb 2002 and first published on 12 Mar 2002


Article type: Paper
DOI: 10.1039/B110481K
Citation: J. Chem. Soc., Dalton Trans., 2002,0, 1521-1527
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    “Bidentate” and “tridentate” sulfonamide ligands for titanium complexes: crystal structures and solution dynamics elucidating an η2 or η3-coordination mode

    S. Hamura, T. Oda, Y. Shimizu, K. Matsubara and H. Nagashima, J. Chem. Soc., Dalton Trans., 2002, 0, 1521
    DOI: 10.1039/B110481K

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