Two-Coordinate, Late First-Row Transition Metal Amido Derivatives of the Bulky Ligand -N(SiPr i 3 )Dipp (Dipp = 2,6-diisopropylphenyl): Effects of the Ligand on the Stability of Two-Coordinate Copper(II) Complexes
Two-Coordinate, Late First-Row Transition Metal Amido Derivatives of the Bulky Ligand -N(SiPr i 3 )Dipp (Dipp = 2,6-diisopropylphenyl): Effects of the Ligand on the Stability of Two-Coordinate Copper(II) Complexes
复制标题
大配体-N(SiPr i 3 )Dipp (Dipp = 2,6-二异丙基苯基)的双配位后第一行过渡金属氨基衍生物：配体对双配位铜(II)配合物稳定性的影响
DOI：
10.1021/acs.inorgchem.9b01159
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发表时间：
2019
影响因子：
4.6
通讯作者：
Power, Philip P.
中科院分区：
文献类型：
--
作者：
Wagner, Clifton L.;Tao, Lizhi;Fettinger, James C.;Britt, R. David;Power, Philip P.
报道了准线性金属(II)双(酰胺)M{N(SiPri3)Dipp}2[Dipp=C6H3-2，6-Pri3；M=Fe(1)，Co(2)，或Zn(3)]的合成、光谱、结构和磁性表征。磁性数据显示了金属配体π-相互作用对这些双配位过渡金属酰胺磁性的影响。具有配体-N(SiPri3)Dipp的铜(I)酰胺物种歧化得到[(Pri3Si)N(c-C6H2-2，6-Pri2)]2(4)。不稳定的双配位铜{N(SiMe3)Dipp}2的电子顺磁共振谱显示出明显低于稳定的双配位铜(II)物种Cu{N(SiMe3)Dipp}2的铜-氮键共价性。对-N(SiPri3)Dipp和其他一系列相关的大体积酰胺配体及其铜衍生物的测试突出了Wigley配体-N(SiMe3)Dipp的空间和电子性质的特殊组合，使其能够稳定独特的两配位铜(II)配合物铜{N(SiMe3)Dipp}2。
The synthesis and spectroscopic, structural, and magnetic characterization of the quasi-linear metal(II) bis(amides) M{N(SiPri3)Dipp}2[Dipp = C6H3-2,6-Pri3; M = Fe (1), Co (2), or Zn (3)] are described. The magnetic data demonstrate the impact of metal ligand π-interactions on the magnetic properties of these two-coordinate transition metal amides. Disproportionation of the copper(I) amide species featuring the ligand -N(SiPri3)Dipp resulted in the decomposition product [(Pri3Si)N(c-C6H2-2,6-Pri2)]2(4). The electron paramagnetic resonance spectrum of the unstable two-coordinate Cu{N(SiPri3)Dipp}2displays significantly less Cu–N bond covalency than the stable two-coordinate copper(II) species Cu{N(SiMe3)Dipp}2. The testing of -N(SiPri3)Dipp and a range of other, related bulky amide ligands with their copper derivatives highlights the peculiar combination of steric and electronic properties of the Wigley ligand -N(SiMe3)Dipp that enable it to stabilize the unique two-coordinate copper(II) complex Cu{N(SiMe3)Dipp}2.