五配位十六电子锰（I）配合物的合成、反应性及π-供体配体复分解反应：[Mn(CO(3)(-TeC(6)H(4)-o-NH-)](-)、[(Mn(CO)(3))2(mu-SC(6)H(4)-o-S--S--C(6)H(4)-o-mu-S--)]、[(CO)(3)Mn(mu-SC(6)H(4)-o-NH(2)-)]2及[(CO)(3)Mn(mu-SC(8)N(2)H(4)-o-S-)](2)(2-)的晶体结构

Syntheses, reactivity, and pi-donating ligand metathesis reaction of five-coordinate sixteen-electron manganese(I) complexes: crystal structures of [Mn(CO(3)(-TeC(6)H(4)-o-NH-)](-), [(Mn(CO)(3))2(mu-SC(6)H(4)-o-S--S--C(6)H(4)-o-mu-S--)], [(CO)(3)Mn(mu-SC(6)H(4)-o-NH(2)-)]2, and [(CO)(3)Mn(mu-SC(8)N(2)H(4)-o-S-)](2)(2-).

作者信息

Liaw W F, Hsieh C K, Lin G Y, Lee G H

机构信息

Department of Chemistry, National Changhua University of Education, Changhua 50058, Taiwan.

出版信息

Inorg Chem. 2001 Jul 2;40(14):3468-75. doi: 10.1021/ic000795a.

DOI:10.1021/ic000795a

PMID:11421694

Abstract

The preparation of the varieties of five-coordinate sixteen-electron manganese(I) complexes Mn(CO)(3)(-EC(6)H(4)-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) pi-donating ligand metathesis reaction of complex Mn(CO)(3)(-TeC(6)H(4)-o-NH-), and (c) reduction /deprotonation of the neutral dimetallic [(Mn(CO)(3))(2)(mu-SC(6)H(4)-o-S-S-C(6)H(4)-o-mu-S-)]/(CO)(3)Mn(mu-SC(6)H(4)-o-NH(2)-) proved successful approaches in this direction. The IR nu(CO) data of the coordinatively and electronically unsaturated Mn(CO)(3)(-EC(6)H(4)-o-E'-) (E = Te, Se, S, O; E' = NH, S, O) complexes suggest the relative order of pi-donating ability of the series of bidentate ligands being TeC(6)H(4)-o-NH(-) > SeC(6)H(4)-o-NH(-) > SC(6)H(4)-o-NH(-) > SC(6)H(4)-o-S(-) > SC(6)H(4)-o-O(-) > OC(6)H(4)-o-O(-). Proton NMR spectra of the Mn(CO)(3)(-EC(6)H(4)-o-NH-) (E = Te, Se, S) derivatives show the low-field shift of the amide proton ((1)H NMR (C(4)D(8)O): delta 9.66 (br) ppm (E = Te), 9.32 (br) ppm (E = Se), 8.98 (br) ppm (E = S)). The formation of the dimetallic (CO)(3)Mn(mu-SC(8)N(2)H(4)-o-S-)(2-) can be interpreted as coordinative association of two units of unstable mononuclear (CO)(3)Mn(-SC(8)N(2)H(4)-o-S-) and reflects the pi-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)(mu-SC(6)H(4)-o-S-S-C(6)H(4)-o-mu-S-)] with internal S-S bond length of 2.222(1) A and the five-coordinate sixteen-electron complex Mn(CO)(3)(-SC(6)H(4)-o-S-) are chemically interconvertible. In a similar fashion, treatment of complex Mn(CO)(3)(-SC(6)H(4)-o-NH-) with HBF(4) yielded neutral dinuclear complex (CO)(3)Mn(mu-SC(6)H(4)-o-NH(2)-) and showed that the amine deprotonation is reversible. Investigations of pi-donating ligand metathesis reactions of complex Mn(CO)(3)(-TeC(6)H(4)-o-NH-) revealed that the stable intermediate, not the pi-donating ability of bidentate ligands, is responsible for the final protonation/oxidation product. This argument is demonstrated by reaction of Mn(CO)(3)(-TeC(6)H(4)-o-NH-) with 1,2-benzenedithiol, hydroxythiophenol, and catechol, respectively leading to the formation of Mn(CO)(3)(-EC(6)H(4)-o-E'-) (E = S, O; E' = S, O), although any pi-donor containing the amido group is a more effective donor than any other pi-donor lacking an amido group. Also, the reactions of Mn(CO)(3)(-TeC(6)H(4)-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 Mn(I)-N bond length of the distorted trigonal bipyramidal Mn(CO)(3)(-TeC(6)H(4)-o-NH-).

摘要

通过以下方法成功制备了五配位十六电子锰（I）配合物Mn(CO)(3)(-EC(6)H(4)-o-E'-)（E = Te、Se、S、O；E' = NH、S、O）的多种变体：（a）将2-氨基苯基二硫属元素化物氧化加成到阴离子锰（0）-羰基上；（b）配合物Mn(CO)(3)(-TeC(6)H(4)-o-NH-)的π-供体配体复分解反应；（c）中性双金属[(Mn(CO)(3))(2)(μ-SC(6)H(4)-o-S-S-C(6)H(4)-o-μ-S-)]/(CO)(3)Mn(μ-SC(6)H(4)-o-NH(2)-)的还原/去质子化。配位和电子不饱和的Mn(CO)(3)(-EC(6)H(4)-o-E'-)（E = Te、Se、S、O；E' = NH、S、O）配合物的红外ν(CO)数据表明，该系列双齿配体的π-供体能力的相对顺序为TeC(6)H(4)-o-NH(-) > SeC(6)H(4)-o-NH(-) > SC(6)H(4)-o-NH(-) > SC(6)H(4)-o-S(-) > SC(6)H(4)-o-O(-) > OC(6)H(4)-o-O(-)。Mn(CO)(3)(-EC(6)H(4)-o-NH-)（E = Te、Se、S）衍生物的质子核磁共振谱显示酰胺质子的低场位移（(1)H NMR (C(4)D(8)O)：δ 9.66（宽峰）ppm（E = Te），9.32（宽峰）ppm（E = Se），8.9（宽峰）ppm（E = S））。双金属(CO)(3)Mn(μ-SC(8)N(2)H(4)-o-S-)(2-)的形成可解释为两个不稳定单核(CO)(3)Mn(-SC(8)N(2)H(4)-o-S-)单元的配位缔合，这反映了双齿配体的π-供体能力对五配位十六电子锰（I）羰基配合物的形成起作用。中性双金属锰（I）-双巯基苯基二硫化物配合物[(Mn(CO)(3))(2)(μ-SC(6)H(4)-o-S-S-C(6)H(4)-o-μ-S-)]，其内部S-S键长为2.222(1) Å，与五配位十六电子配合物Mn(CO)(3)(-SC(6)H(4)-o-S-)在化学上可相互转化。类似地，用HBF(4)处理配合物Mn(CO)(3)(-SC(6)H(4)-o-NH-)得到中性双核配合物(CO)(3)Mn(μ-SC(6)H(4)-o-NH(2)-)，表明胺的去质子化是可逆的。对配合物Mn(CO)(3)(-TeC(6)H(4)-o-NH-)的π-供体配体复分解反应的研究表明，稳定的中间体而非双齿配体的π-供体能力决定了最终的质子化/氧化产物。Mn(CO)(3)(-TeC(6)H(4)-o-NH-)分别与1,2-苯二硫醇、羟基苯硫酚和邻苯二酚反应，生成Mn(CO)(3)(-EC(6)H(4)-o-E'-)（E = S、O；E' = S、O），证明了这一观点，尽管任何含酰胺基的π-供体都比任何不含酰胺基的其他π-供体更有效。此外，Mn(CO)(3)(-TeC(6)H(4)-o-NH-)与亲电试剂在电子密度更高的酰胺位点发生的反应支持了螯合的2-碲醇基苯基酰胺中电子密度更高的酰胺供体占据赤道位点，这由扭曲的三角双锥Mn(CO)(3)(-TeC(6)H(4)-o-NH-)较短的Mn(I)-N键长表明。