A New Donor Atom System [(SNN)(S)] for the Synthesis of Neutral Oxotechnetium(V) Mixed-Ligand Complexes.
A New Donor Atom System [(SNN)(S)] for the Synthesis of Neutral Oxotechnetium(V) Mixed-Ligand Complexes.
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用于合成中性氧锝(V)混合配体配合物的新供体原子系统[(SNN)(S)]。
DOI：
10.1021/ic9513649
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发表时间：
1996
影响因子：
4.6
通讯作者：
E. Chiotellis
中科院分区：
文献类型：
--
作者：
M. Papadopoulos;M. Pelecanou;I. Pirmettis;D. M. Spyriounis;C. Raptopoulou;A. Terzis;C. I. Stassinopoulou;E. Chiotellis
本文报道了一种以含SNN给体和多种单齿硫醇为配体（L2H）的配体（L1H(2)）为配体的通式TcOL1L2“3 + 1”混合配体氧锝配合物的新方法。配体L1H(2)(1-3，通式R(1)CH(2)CH(2)NHCH(2)C(R(2))(2)SH，其中R(1) = N(CH(3))(2) = H， R(1) =吡咯烷-1-基，R(2) = H， R(1) =吡咯烷-1-基，R(2) = H， R(1) =吡咯烷-1-基，R(2) = CH(3))， R(1) =吡咯烷-1-基，R（2) = CH(3)）在3中作为三叉SNN螯合物与TcO（3+）核，留下一个开放的配位位顺式氧基。在单齿硫醇（L2H）存在下，以（99）Tc(V)-葡萄糖酸盐为前体，空位被作为配体的硫醇填充。该方法通过L1H(2)和L2H与Tc(V)-葡萄糖酸盐以1:1:1的比例反应，制备了4种中性氧锝配合物(4-7，通式TcO[R(1)CH(2)CH(2)NCH(2)C(R（2))(2)S][SR]，其中RSH =对甲氧基苯硫醇或对甲基苯硫醇或苄基硫醇）。用元素分析和光谱方法对配合物进行了表征。所有配合物都完成了(1)H和（13）C的核磁共振分配。x射线晶体学研究表明，5种配合物(R（1) =吡啶烷-1-基，R(2) = H, RSH =对甲基苯硫醇）和7种配合物(R(1) =哌啶烷-1-基，R（2) = CH(3), RSH =苄基硫醇）在P2(1)/n单斜空间群中结晶(a = 10.223(1) Å， b = 9.283(1) Å， c = 18.337(2) Å， β = 97.262(2)度，V = 1726.3(4) Å(3), Z = 4；a = 11.876(2) Å， b = 10.470(2) Å， c = 17.098(3) Å， beta = 105.990(4)度，V = 2043.8（6) Å(3), Z = 4，分别为5和7）。配合物5和7与氧配体在轴向位置具有扭曲的方锥体配位几何。在这两个配合物中，氧基的空间要求导致Tc原子在NNSS给原子的平均赤道平面外位移0.68 Å。
A new approach to the "3 + 1" mixed ligand oxotechnetium complexes of the general formula TcOL1L2, with ligands (L1H(2)) containing the SNN donor set and various monodentate thiols as coligands (L2H) is reported. The ligands L1H(2) (1-3, general formula R(1)CH(2)CH(2)NHCH(2)C(R(2))(2)SH where R(1) = N(CH(3))(2) and R(2) = H in 1, R(1) = pyrrolidin-1-yl and R(2) = H in 2, and R(1) = piperidin-1-yl and R(2) = CH(3) in 3) act as tridentate SNN chelates to the TcO(3+) core, leaving open one coordination site cis to the oxo group. In the presence of a monodentate thiol (L2H) and using (99)Tc(V)-gluconate as precursor, the vacancy is filled by the thiol which acts as the coligand. With this approach four neutral oxotechnetium complexes (4-7, general formula TcO[R(1)CH(2)CH(2)NCH(2)C(R(2))(2)S][SR] where RSH = p-methoxybenzenethiol, or p-methylbenzenethiol or benzyl mercaptan) were prepared in high yield by reacting L1H(2) and L2H with Tc(V)-gluconate in a ratio 1:1:1. The complexes were characterized by elemental analysis and spectroscopic methods. Complete assignments of (1)H and (13)C NMR resonances were made for all complexes. X-ray crystallographic studies of 5 (R(1) = pyrrolidin-1-yl, R(2) = H, RSH = p-methylbenzenethiol) and 7 (R(1) = piperidin-1-yl, R(2) = CH(3), RSH = benzyl mercaptan) showed that the complexes crystallize in the monoclinic space group P2(1)/n (a = 10.223(1) Å, b = 9.283(1) Å, c = 18.337(2) Å, beta = 97.262(2) degrees, V = 1726.3(4) Å(3), Z = 4; a = 11.876(2) Å, b = 10.470(2) Å, c = 17.098(3) Å, beta = 105.990(4) degrees, V = 2043.8(6) Å(3), Z = 4, for 5 and 7, respectively). Complexes5 and 7 have distorted square pyramidal coordination geometry with the oxo ligand in the axial position. The steric requirements of the oxo group cause the Tc atom to be displaced 0.68 Å out of the mean equatorial plane of the NNSS donor atoms in both complexes.