Ligand-Centered Triplet Diradical Supported by a Binuclear Palladium(II) Dipyrrindione
نویسندگان
چکیده
Oligopyrroles form a versatile class of redox-active ligands and electron reservoirs. Although the stabilization radicals within oligopyrrolic π systems is more common for macrocyclic ligands, bidentate dipyrrindiones are emerging as compact platforms one-electron redox chemistry in transition-metal complexes. We report synthesis bis(aqua) palladium(II) dipyrrindione complex its deprotonation-driven dimerization to hydroxo-bridged binuclear presence water or triethylamine. Electrochemical, spectroelectrochemical, computational analyses indicate accessibility two quasi-reversible ligand-centered reduction processes. The product two-electron chemical by cobaltocene was isolated characterized. In solid state, this cobaltocenium salt features folded dianionic that maintains hydroxo bridges between divalent palladium centers. X-band Q-band EPR spectroscopic experiments DFT analysis allow assignment species diradical with spin density almost entirely located on ligands. As established from temperature dependence, associated exchange coupling weak antiferromagnetic (J ≈ −2.5 K), which results predominantly triplet state at temperatures measurements have been performed.
منابع مشابه
Stable diarylnitroxide diradical with triplet ground state.
Nitroxide diradical , the first isolated diarylnitroxide diradical, is stable in the solid state at room temperature and it possesses triplet ground state with strong ferromagnetic coupling.
متن کاملsynthesis of binuclear platinum complexes containing biphosphine ligand
هدف از این مطالعه طراحی یک روش کلی برای سنتز یک سری از کمپلکس های دو هسته ای متقارن سیکلومتاله شده پلاتین (ii) بوده که دارای یک لیگاند پل زن(1,2-bis[bis(pentafluoro-phenyl)phosphino]ethane),dfppe, است. از واکنش cis-[pt(r)2(sme2)2]، که در آنr= para-tolyl ، با یک اکی والان از لیگاند benzo[h]quinoline,bhq، در استون محصول [pt(r)(bhq)(sme2)] که در آن r= para-tolyl بدست می آید. همچنین از واکنش 5/0 اک...
A dimeric aluminium hydroxide supported by a new disiloxide ligand.
The synthesis and structure of a dimeric aluminium hydroxide complex containing the novel chelating 1,4-disiloxide ligand [CH(2){Me(Me(3)Si)(2)Si}(2)SiO](2)(2-) (2)-2H is reported. [CH(2){Me(Me(3)Si)(2)Si}(2)SiO](2)AlOH (4) was prepared by careful hydrolysis of [CH(2){Me(Me(3)Si)(2)Si}(2)SiO](2)AlMe·THF (3).
متن کاملThermally controlling the singlet-triplet energy gap of a diradical in the solid state.
Diradicals, molecules with two unpaired electrons, are reactive intermediates that play an important role in many fields. Their defining feature is the energy difference between their singlet and triplet states, which provides direct information on the extent of their electron exchange interactions. Such knowledge is essential for understanding their diradical character, which is controllable i...
متن کاملذخیره در منابع من
با ذخیره ی این منبع در منابع من، دسترسی به آن را برای استفاده های بعدی آسان تر کنید
ژورنال
عنوان ژورنال: Inorganic Chemistry
سال: 2021
ISSN: ['0020-1669', '1520-510X']
DOI: https://doi.org/10.1021/acs.inorgchem.1c01691