η5-semiquinone and η4-quinone complexes of manganese tricarbonyl.: Intermolecular hydrogen bonding in the solid state and in solution

被引：41

作者：

Oh, M ^{[1
]}

Carpenter, GB ^{[1
]}

Sweigart, DA ^{[1
]}

机构：

[1] Brown Univ, Dept Chem, Providence, RI 02912 USA

来源：

ORGANOMETALLICS | 2002年 / 21卷 / 06期

关键词：

D O I：

10.1021/om011024x

中图分类号：

O61 [无机化学];

学科分类号：

070301 ; 081704 ;

摘要：

Cationic manganese tricarbonyl complexes containing eta(6)-hydroquinone (1a), eta(6)-catechol (2a), and eta(6)-resorcinol (3a) ligands are readily deprotonated in DMSO with triethylamine or other weak bases to afford stable (eta(5)-semiquinone)Mn(CO)(3) (1b-3b) and (eta(4)-quinone)Mn(CO)(3)(-) (1c-3c) complexes. The relative acidity in DMSO follows the qualitative order 2a > 3a > 1a. NMR spectra of the semiquinones 1b-3b indicate dynamic, strong hydrogen bonding in solution. The crystal structures of 1b and 2b feature strong intermolecular hydrogen bonding, resulting in polymers with 1b and dimers with 2b. Deprotonation of 1a-3a or 1b-3b with sodium acetate in DMSO allowed the isolation and characterization of the eta(4)-quinone salts Na[1c-3c].3H(2)O. The crystal structure of Na(2c].3H(2)O shows the sodium cation to be bonded to just one quinone oxygen, IR and crystal structure data of both eta(5)-semiquinone and eta(4)-quinone complexes provide clear evidence of significant contributions to the overall structure from more polar eta(6)-resonance forms.

引用

页码：1290 / 1295

页数：6

共 40 条

[21] η4-quinone, η5-semiquinone and η6-hydroquinone complexes of pentamethylcyclopentadienyl iridium.: X-ray molecular structure of [Cp*Ir(η4-1,4 benzoquinone)] [J].