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首页> 外文期刊>Dalton transactions: An international journal of inorganic chemistry >Transition metal complexes containing the S(NtBu)_4~(2?) tetraimidosulfate dianion
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Transition metal complexes containing the S(NtBu)_4~(2?) tetraimidosulfate dianion

机译:含有S(NtBu)_4〜(2?)四亚氨基硫酸二价阴离子的过渡金属配合物

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摘要

Three novel metal complexes [(acac)_2Cu_2(NtBu)_4S] (3), [Li(thf)_4]_2[I_4Cd_2(NtBu)_4S] (4) and [(thf)_2Li{(SiMe_3)_2N}-Zn(NtBu)_4S] (5) are prepared from the intended transmetalation of the dilithium complex of N,N’,N’’,N’’’-tetrakis(tert-butyl)tetraimidosulfate [(thf)_4Li_2(NtBu)_4S] (1). The two lithium cations are replaced by either the cationic (acac)Cu(II) moiety, the neutral I_2Cd(II) residue or only a single lithium cation is substituted by the cationic (Me_3Si)_2NZn(II) fragment. The complexes show two main results: first the S(NtBu)_4~(2?) tetrahedron can serve as a ligand to transition metals from the soft Cu(II) to the harder Zn(II) at opposite sides and second the S–N bond distances vary only marginally in response to the various metals and the four distances constantly sum up to 6.38(2) ?. Hence the electropositive sulfur atom responds by internal shift to the metal-polarized negative charge at the outside of the S(NR)_4~(2?) tetrahedron.
机译:三种新型金属配合物[(acac)_2Cu_2(NtBu)_4S](3),[Li(thf)_4] _2 [I_4Cd_2(NtBu)_4S](4)和[(thf)_2Li {(SiMe_3)_2N} -Zn (NtBu)_4S](5)由N,N',N'',N'''-四(叔丁基)四亚氨基硫酸盐[(thf)_4Li_2(NtBu)_4S]的双锂配合物的预期的金属转移反应制得(1)。两个锂阳离子被阳离子(acac)Cu(II)部分,中性I_2Cd(II)残基取代,或仅单个锂阳离子被阳离子(Me_3Si)_2NZn(II)片段取代。配合物显示出两个主要结果:首先,S(NtBu)_4〜(2?)四面体可以用作配体,使金属在相对侧从软Cu(II)过渡到较硬的Zn(II),其次是S– N键的距离仅随各种金属的变化而略有变化,四个距离的总和为6.38(2)Ω。因此,正电性硫原子通过内部位移对S(NR)_4〜(2?)四面体外部的金属极化负电荷作出反应。

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