A Versatile Dinucleating Ligand Containing Sulfonamide Groups

详细信息    查看全文

• 作者：Jonas Sundberg ; Hannes Witt ; Lisa Cameron ; Mikael H氓kansson ; Jesper Bendix ; Christine J. McKenzie
• 刊名：Inorganic Chemistry
• 出版年：2014
• 出版时间：March 17, 2014
• 年：2014
• 卷：53
• 期：6
• 页码：2873-2882
• 全文大小：465K
• 年卷期：v.53,no.6(March 17, 2014)
• ISSN：1520-510X

文摘

Copper, iron, and gallium coordination chemistries of the new pentadentate bis-sulfonamide ligand 2,6-bis(N-2-pyridylmethylsulfonamido)-4-methylphenol (psmpH₃) were investigated. PsmpH₃ is capable of varying degrees of deprotonation, and notably, complexes containing the fully trideprotonated ligand can be prepared in aqueous solutions using only divalent metal ions. Two of the copper(II) complexes, [Cu₂(psmp)(OH)] and [Cu₂(psmp)(OAc)₂]^{鈭?/sup>, demonstrate the anticipated 1:2 ligand/metal stoichiometry and show that the dimetallic binding site created for exogenous ligands possesses high inherent flexibility since additional one- and three-atom bridging ligands bridge the two copper(II) ions in each complex, respectively. This gives rise to a difference of 0.4 脜 in the Cu路路路Cu distances. Complexes with 2:3 and 2:1 ligand/metal stoichiometries for the divalent and trivalent metal ions, respectively, were observed in [Cu₃(psmp)₂(H₂O)] and [M(psmpH)(psmpH₂)], where M = GaIII, FeIII. The deprotonated tridentate N-2-pyridylsulfonylmethylphenolato moieties chelate the metal ions in a meridional fashion, whereas in [Cu₃(psmp)₂(H₂O)] the rare 渭₂-N-sulfonamido bridging coordination mode is observed. In the bis-ligand mononuclear complexes, one picolyl arm of each ligand is protonated and uncoordinated. Magnetic susceptibility measurements on the doubly and triply bridged dicopper(II) complexes indicate strong and medium strength antiferromagnetic coupling interactions, with J = 234 cm鈥? and 115 cm鈥? for [Cu₂(psmp)(OH)] and [Cu₂(psmp)(OAc)₂]鈭?/sup>, respectively (in H_HDvV =...+JS₁S₂ convention). The trinuclear [Cu₃(psmp)₂(H₂O)], in which the central copper ion is linked to two flanking copper atoms by two 渭₂-N-sulfonamido bridges and two phenoxide bridges shows an overall magnetic behavior of antiferromagnetic coupling. This is corroborated computationally by broken-symmetry density functional theory, which for isotropic modeling of the coupling predicts an antiferromagnetic coupling strength of J = 70.5 cm鈥?.}