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题名: Syntheses, Reactivity, and π-Donating Ligand Metathesis Reaction of Five-Coordinate Sixteen-Electron Manganese(I) Complexes: Crystal Structures of [Mn(CO)3(-TeC6H4-o-NH-)]-, [(Mn(CO)3)2(µ-SC6H4-o-S-S-C6H4-o-µ-S-)], [(CO)3Mn(µ-SC6H4-o-NH2-)]2, and [(CO)3Mn(µ-SC8N2H4-o-S-)]2 2-
作者: Liaw, Wen-Feng;Hsieh, Chien-Kuo;Lin, Ging-Yi;Lee, Gene-Hsiang
贡献者: 化學系
日期: 2001
上传时间: 2012-11-21T07:16:36Z
出版者: American Chemical Society
摘要: The preparation of the varieties of five-coordinate sixteen-electron manganese(I) complexes [Mn(CO)3(-EC6H4-
o-E�-)]- (E ) Te, Se, S, O; E� ) NH, S, O) by (a) oxidative addition of 2-aminophenyl dichalcogenides to
anionic manganese(0)-carbonyl, (b) �-donating ligand metathesis reaction of complex [Mn(CO)3(-TeC6H4-o-
NH-)]-, and (c) reduction /deprotonation of the neutral dimetallic [(Mn(CO)3)2(�-SC6H4-o-S-S-C6H4-o-�-S-
)]/[(CO)3Mn(�-SC6H4-o-NH2-)]2 proved successful approaches in this direction. The IR �CO data of the
coordinatively and electronically unsaturated [Mn(CO)3(-EC6H4-o-E�-)]- (E ) Te, Se, S, O; E� ) NH, S, O)
complexes suggest the relative order of �-donating ability of the series of bidentate ligands being [TeC6H4-o-
NH]2- > [SeC6H4-o-NH]2- > [SC6H4-o-NH]2- > [SC6H4-o-S]2- > [SC6H4-o-O]2- > [OC6H4-o-O]2-. Proton
NMR spectra of the [Mn(CO)3(-EC6H4-o-NH-)]- (E ) Te, Se, S) derivatives show the low-field shift of the
amide proton (1H NMR (C4D8O): � 9.66 (br) ppm (E ) Te), 9.32 (br) ppm (E ) Se), 8.98 (br) ppm (E ) S)).
The formation of the dimetallic [(CO)3Mn(�-SC8N2H4-o-S-)]2
2- can be interpreted as coordinative association
of two units of unstable mononuclear [(CO)3Mn(-SC8N2H4-o-S-)]- and reflects the �-donating ability of the
bidentate ligand is responsible for the formation of pentacoordinate, sixteen-electron manganese(I) carbonyl
complexes. The neutral bimetallic manganese(I)-bismercaptophenyl disulfide complex [(Mn(CO)3)2(�-SC6H4-o-
S-S-C6H4-o-�-S-)] with internal S-S bond length of 2.222(1) � and the five-coordinate sixteen-electron complex
[Mn(CO)3(-SC6H4-o-S-)]- are chemically interconvertible. In a similar fashion, treatment of complex [Mn(CO)3-
(-SC6H4-o-NH-)]- with HBF4 yielded neutral dinuclear complex [(CO)3Mn(�-SC6H4-o-NH2-)]2 and showed
that the amine deprotonation is reversible. Investigations of �-donating ligand metathesis reactions of complex
[Mn(CO)3(-TeC6H4-o-NH-)]- revealed that the stable intermediate, not the �-donating ability of bidentate ligands,
is responsible for the final protonation/oxidation product. This argument is demonstrated by reaction of [Mn-
(CO)3(-TeC6H4-o-NH-)]- with 1,2-benzenedithiol, hydroxythiophenol, and catechol, respectively leading to
the formation of [Mn(CO)3(-EC6H4-o-E�-)]- (E ) S, O; E� ) S, O), although any �-donor containing the
amido group is a more effective donor than any other �-donor lacking an amido group. Also, the reactions of
[Mn(CO)3(-TeC6H4-o-NH-)]- with electrophiles occurring at the more electron-rich amide site support that the
more electron-rich amide donor of the chelating 2-tellurolatophenylamido occupies an equatorial site as indicated
by a shorter MnI-N bond length of the distorted trigonal bipyramidal [Mn(CO)3(-TeC6H4-o-NH-)]-.
關聯: Inorg. Chem., 40(14): 3468-3475
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