Georg-August-Universität, Institut für Anorganische Chemie, Tammannstr. 4, 37077 Göttingen, Germany.
Dalton Trans. 2014 Mar 21;43(11):4506-13. doi: 10.1039/c3dt53304b.
The iridium(II) complex [IrCl{N(CHCHPtBu2)2}] is reduced by KC8 to give the anionic iridium(I) pincer complex IrCl{N(CHCHPtBu2)2} which was isolated and fully characterized upon stabilization of the counter cation with crown ether as [K(15-cr-5)2][IrCl{N(CHCHPtBu2)2}]. This unprecedented anionic iridium(I) pincer complex completes the unusual, structurally characterized Ir(I)/Ir(II)/Ir(III) redox series IrCl{N(CHCHPtBu2)2}, all in a square-planar coordination geometry, emphasizing the versatility of this PNP pincer ligand in stabilizing a broad range of oxidation states. The anionic chloro complex is a versatile source of the Ir(PNP) platform. Its reactivity was examined towards chloride ligand substitution against CO and N2, and oxidative addition of C-electrophiles, C-H bonds and dioxygen, allowing for the isolation of iridium(I) and iridium(III) (PNP) carbonyl, hydrocarbyl and peroxo complexes which were spectroscopically and crystallographically characterized.
铱（II）配合物[IrCl{N(CHCHPtBu2)2}]被 KC8 还原为阴离子铱（I）钳形配合物IrCl{N(CHCHPtBu2)2}，该配合物通过用冠醚稳定抗衡阳离子而分离并进行了充分的表征，得到[K(15-cr-5)2][IrCl{N(CHCHPtBu2)2}]。这种前所未有的阴离子铱（I）钳形配合物完成了不寻常的、结构表征的 Ir(I)/Ir(II)/Ir(III)氧化还原系列IrCl{N(CHCHPtBu2)2}, 所有这些都具有正方形平面配位几何形状，强调了这种 PNP 钳形配体在稳定广泛的氧化态方面的多功能性。阴离子氯配合物是 Ir(PNP)平台的多功能来源。研究了其对 CO 和 N2 的配体取代反应性，以及 C-亲电试剂、C-H 键和氧气的氧化加成反应性，从而可以分离出铱（I）和铱（III）（PNP）羰基、烃基和过氧配合物，并对其进行了光谱和晶体学表征。
