Crown Thioether Complexes of Low-valent Transition Metals

低价过渡金属冠硫醚配合物

基本信息

批准号：
60470048
负责人：
YOSHIDA Toshikatsu
金额：
$ 3.78万
依托单位：
University of Osaka Prefecture
依托单位国家：
日本
项目类别：
Grant-in-Aid for General Scientific Research (B)
财政年份：
1985
资助国家：
日本
起止时间：
1985 至 1987
项目状态：
已结题

项目摘要

Avariety of low-valent transition metal complexes of crown thioethers such as 1,4,8,11-tetrathia- cycloteetradecane ([14]aneS_4), its 6,6,13,13-tetramethyl analogue (Me_4[14]aneS_4), 1,5,9,13-terathiachclo-hexadecane ([16]aneS_4), and its 3,3,7,7,11,11,15,15-octamethy analogue (Me_8[16]aneS_4) have been prepared. They are RhL^+ (L=R_4[14]aneS_4, R_8[16]aneS_4), cis- and trans-RuCl_<>L (L=R_4[14]aneS_4,R_8[16]aneS_4), trans-RuH(C1)L (L=Me_4[14]aneS_4,Me_8[16]aneS_4), trans-RuH(BH_4,Ru_2H(C1)(<nu>-H) [Me_4[14]aneS_4]_2^+, and trans-MoL_2Me_8[16]aneS_4 (L'=Cl, Br, N_2, CO, HC<congruent>CH, PhC<congruent>CH, CH_2=CH_2). The elctrochemical, spectral, and x-ray structural studies of these complexes as well as extended Huckel MO calculations on the models, RH(SH_2)_4)^+ and trans-Mo(N_2)_2(SH_2)_4 revealed that the crown thioethers behave as p_<<pi>> donor ligand. this eelctronic feature of the crown thioether was further verified by the facile oxidative addition of CH_2Cl_2 to give trans-RHCl(CH_2Cl)L^+ and also by an unpercedented direct arylation of the coordinated N_2 molecule in trans-Mo(N_2)_2Me_8[16]aneS_4 with PhX under ambient conditions affording trans-MoX(N_2Ph)Me_8[16]-aneS_4 (X=Br, I). The chemical properties of the above complexes are found to be affected by the ring size of the macrocycles and the geometry of the complexes. For example, a reaction of cis-RuCl_2R_4[14]-aneS_4 with Al_2Me_6 in aromatic hydrocarbons proceeds through an intermolecular C(sp^2)-H bond activation to give trans-RuCl(Ar)R_4[14]aneS_4 (Ar=Ph, tolyl), while a similar reaction of trans-isomer afforded trans-MoCl(Me)Me_4[14]aneS_4. By contrast, cis-RuCl_2Me_8[16]aneS_4 gave an expected RuCl(Me_8[16]aneS_4. It is to be noted that trans-Mo(N_2)_2Me_8[16]aneS_4 represents the first example of dinitrogen complex containing only sulfur ligand which has been long desired to prepared as a chemical model to mimic the function of nitrogenase.

各种冠硫醚的低价过渡金属配合物，如1,4,8,11-四硫-环十四烷([14]aneS_4)，其6,6,13,13-四甲基类似物(Me_4[14]aneS_4)， 1,5,9,13-terathiachclo-hexadecane ([16]aneS_4)，及其已制备出3,3,7,7,11,11,15,15-八甲基类似物(Me_8[16]aneS_4)。它们是RhL^+ (L=R_4[14]aneS_4, R_8[16]aneS_4)、顺式和反式RuCl_<>L (L=R_4[14]aneS_4,R_8[16]aneS_4)、反式RuH( C1)L (L=Me_4[14]aneS_4,Me_8[16]aneS_4),反式 RuH(BH_4,Ru_2H(C1)(<nu>-H) [Me_4[14]aneS_4]_2^+ 和反式 MoL_2Me_8[16]aneS_4 (L'=Cl、Br、N_2、CO、HC<同余>CH、PhC<同余>CH、CH_2=CH_2)。这些配合物的结构研究以及对模型 RH(SH_2)_4)^+ 和反式 Mo(N_2)_2(SH_2)_4 的扩展 Huckel MO 计算表明，冠硫醚表现为 p_<<pi>> 供体配体。通过 CH_2Cl_2 的轻松氧化加成得到反式 RHCl(CH_2Cl)L^+ 以及反式 Mo(N_2)_2Me_8 中配位的 N_2 分子前所未有的直接芳基化进一步验证了冠硫醚的这种电子特征[16 ]aneS_4 与 PhX 在环境条件下提供反式 MoX(N_2Ph)Me_8[16]-aneS_4 (X=Br，I)。发现上述配合物的化学性质受到大环的环尺寸和配合物的几何形状的影响。例如，顺式-RuCl_2R_4[14]-aneS_4与Al_2Me_6在芳香烃中通过分子间C(sp^2)-H键活化进行反应，得到反式-RuCl(Ar)R_4[14]aneS_4 (Ar=Ph ，甲苯基），而反式异构体的类似反应则得到反式-MoCl(Me)Me_4[14]aneS_4。相比之下，顺式RuCl_2Me_8[16]aneS_4给出了预期的RuCl(Me_8[16]aneS_4。值得注意的是，反式Mo(N_2)_2Me_8[16]aneS_4代表仅含有硫配体的二氮络合物的第一个例子，长期以来人们一直希望制备一种化学模型来模拟固氮酶的功能。