Solid-State Structure and Solution Behavior of Eight-Coordinate Sm(III) Poly(pyrazolyl)borate Compounds
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- 作者：Irene Lopes ; Anna C. Hillier ; Sung Ying Liu ; Â ; ngela Domingos ; José ; Ascenso ; Adelino Galvã ; o ; Andrea Sella ; and Noé ; mia Marques
- 刊名：Inorganic Chemistry
- 出版年：2001
- 出版时间：March 12, 2001
- 年：2001
- 卷：40
- 期：6
- 页码：1116 - 1125
- 全文大小：189K
- 年卷期：v.40,no.6(March 12, 2001)
- ISSN：1520-510X
文摘
[Sm(TpMe2)2(
2-S2CNR2)] compounds (R = Et (1), Me (2); TpMe2 = HB(3,5-Me2pz)3) have been isolated fromreaction of (R2NC(S)S)2 with 2 equiv of [Sm(TpMe2)2]. Reductive cleavage of 2,2'-dipyridyl disulfide or 2,2'-dipyridyl diselenide by [Sm(TpMe2)2] afforded good yields of [Sm(TpMe2)2(2-Y)] compounds (Y = 2-SC5H4N(3), 2-SeC5H4N (4)). 4 is the first selenopyridine complex of an f-block element. Sm(TpMe2)2(2-OC5H4N) (5) hasbeen synthesized by salt metathesis of [Sm(TpMe2)2Cl] with the sodium salt of the 2-hydroxypyridine. The solid-state structures of 1, 3, 4, and 5 were determined by single-crystal X-ray diffraction analysis and revealed that thecompounds are all eight-coordinate with dodecahedral geometry. The samarium atoms are bound in tridentatefashion to two pyrazolylborate ligands and in bidentate fashion by the third ligand. The solution behavior of thecompounds was studied by 1H NMR techniques. 1H-1H exchange spectroscopy experiments give evidence fortwo distinct dynamic regimes occurring in solution.
2-S2CNR2)] compounds (R = Et (1), Me (2); TpMe2 = HB(3,5-Me2pz)3) have been isolated fromreaction of (R2NC(S)S)2 with 2 equiv of [Sm(TpMe2)2]. Reductive cleavage of 2,2'-dipyridyl disulfide or 2,2'-dipyridyl diselenide by [Sm(TpMe2)2] afforded good yields of [Sm(TpMe2)2(2-Y)] compounds (Y = 2-SC5H4N(3), 2-SeC5H4N (4)). 4 is the first selenopyridine complex of an f-block element. Sm(TpMe2)2(2-OC5H4N) (5) hasbeen synthesized by salt metathesis of [Sm(TpMe2)2Cl] with the sodium salt of the 2-hydroxypyridine. The solid-state structures of 1, 3, 4, and 5 were determined by single-crystal X-ray diffraction analysis and revealed that thecompounds are all eight-coordinate with dodecahedral geometry. The samarium atoms are bound in tridentatefashion to two pyrazolylborate ligands and in bidentate fashion by the third ligand. The solution behavior of thecompounds was studied by 1H NMR techniques. 1H-1H exchange spectroscopy experiments give evidence fortwo distinct dynamic regimes occurring in solution.