"Bidentate" and "tridentate" sulfonamide ligands for titanium complexes: Crystal structures and solution dynamics elucidating an η2 or η3-coordination mode

Satoshi Hamura; Takashi Oda; Yasuaki Shimizu; Kouki Matsubara; Hideo Nagashima

doi:10.1039/b110481k

"Bidentate" and "tridentate" sulfonamide ligands for titanium complexes: Crystal structures and solution dynamics elucidating an η² or η³-coordination mode

Satoshi Hamura, Takashi Oda, Yasuaki Shimizu, Kouki Matsubara, Hideo Nagashima

Department of Applied Molecular Chemistry

Research output: Contribution to journal › Article › peer-review

15 Citations (Scopus)

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 η¹/η² 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(NMe ₂)₂ (2) in high yield, in which the sulfonamide moiety was coordinated to the titanium center in an η³ (NON) mode. No sign of η¹/η² 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(NMe ₂)Cl]₂ (4) and [{TsN(CH₂)₂O(CH₂)₂NTs}TiCl ₂]₂ (5). An X-ray structure determination of 4 revealed that sulfonyl oxygen bridging resulted in the formation of an eight membered ring.

Original language	English
Pages (from-to)	1521-1527
Number of pages	7
Journal	Journal of the Chemical Society, Dalton Transactions
Issue number	7
DOIs	https://doi.org/10.1039/b110481k
Publication status	Published - 2002

All Science Journal Classification (ASJC) codes

Chemistry(all)

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10.1039/b110481k

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"Bidentate" and "tridentate" sulfonamide ligands for titanium complexes : Crystal structures and solution dynamics elucidating an η² or η³-coordination mode. / Hamura, Satoshi; Oda, Takashi; Shimizu, Yasuaki; Matsubara, Kouki; Nagashima, Hideo.

In: Journal of the Chemical Society, Dalton Transactions, No. 7, 2002, p. 1521-1527.

Research output: Contribution to journal › Article › peer-review

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title = "{"}Bidentate{"} and {"}tridentate{"} sulfonamide ligands for titanium complexes: Crystal structures and solution dynamics elucidating an η2 or η3-coordination mode",

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 η1/η2 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(NMe 2)2 (2) in high yield, in which the sulfonamide moiety was coordinated to the titanium center in an η3 (NON) mode. No sign of η1/η2 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(NMe 2)Cl]2 (4) and [{TsN(CH2)2O(CH2)2NTs}TiCl 2]2 (5). An X-ray structure determination of 4 revealed that sulfonyl oxygen bridging resulted in the formation of an eight membered ring.",

author = "Satoshi Hamura and Takashi Oda and Yasuaki Shimizu and Kouki Matsubara and Hideo Nagashima",

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AU - Matsubara, Kouki

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N2 - 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 η1/η2 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(NMe 2)2 (2) in high yield, in which the sulfonamide moiety was coordinated to the titanium center in an η3 (NON) mode. No sign of η1/η2 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(NMe 2)Cl]2 (4) and [{TsN(CH2)2O(CH2)2NTs}TiCl 2]2 (5). An X-ray structure determination of 4 revealed that sulfonyl oxygen bridging resulted in the formation of an eight membered ring.

AB - 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 η1/η2 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(NMe 2)2 (2) in high yield, in which the sulfonamide moiety was coordinated to the titanium center in an η3 (NON) mode. No sign of η1/η2 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(NMe 2)Cl]2 (4) and [{TsN(CH2)2O(CH2)2NTs}TiCl 2]2 (5). An X-ray structure determination of 4 revealed that sulfonyl oxygen bridging resulted in the formation of an eight membered ring.

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