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.

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已经准备了3,3,7,7,11,11,15,15-octamethy模拟（ME_8 [16] ANES_4）。它们为rhl^+（l = r_4 [14] anes_4，r_8 [16] anes_4），顺式和trans-rucl _ <> l（l = r_4 [14] anes_4，r_8 [16] anes_4），trans-ruh（trans-ruh（c1）l（l = me_4 [14] [14] [14] [14] anes_4，me_4，me_4，me_8 [16] trans-ruh（bh_4，ru_2h（c1）（<nu> -h）[me_4 [14] anes_4] _2^+和trans-mol_2me_8 [16] anes_4（l'= cl，br，br，n_2，n_2，co，co，co，co，co，hc <Quartuent> gorge> ch Qualuent> ch，phc <Qualte> phc <Qualte>这些复合物的结构研究以及模型上的扩展Huckel MO计算，RH（SH_2）_4）^+和Trans-Mo（N_2）_2（SH_2）_4表明，冠状硫乙烷的表现为P _ << Pi >>供体配体。 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）。发现上述复合物的化学特性受到大环的环尺寸和复合物的几何形状的影响。例如，在芳烃中，顺式-RUCL_2R_4 [14] -ANES_4与al_2me_6的反应通过分子间C（SP^2）-h键激活进行反式rucl（ar-rucl（ar）r_4 [14] r_4 [14] anes_4（ar = pH，tolyl），而跨度的反射率相似（MEES-MEES-MEESER-MEOCER-MEOCER）（MEOC 4）（anes_4）。相比之下，CIS-RUCL_2ME_8 [16] ANES_4给出了预期的RUCL（ME_8 [16] ANES_4。要注意的是，Trans-Mo（n_2）_2Me_8 [16] Anes_4代表了只有长期以来已准备好的化学物质的二硫酸含量的dinitrogen综合体的第一个dinitrogen综合体的例子。