New monomeric O,N-heterocyclic germylene AdAPGe (1) based on 4,6-di-tert-butyl-N-adamantyl-o-aminophenol is synthesized and structurally characterized. Germylene 1 in the crystal demonstrates weak Ge···Ge interactions between adjacent molecules. The redox activity of...
A stable O,N‐heterocyclic stannylene 1 bearing novel tetradentate 2,4‐di‐tert‐butyl‐6‐((2‐(1‐((pyridin‐2‐ylmethyl)imino)ethyl)phenyl)amino)phenolate ligand (RAPH2) was synthesized and characterized. Complex 1 is monomeric in crystal and solution due to two additional intramolecular N → Sn donor–acceptor interactions. The diverse reactivity of compound 1 towards various iron carbonyl compounds was studied. Oxidative addition of [Fe2(μ‐S2)(CO)6]2 to the tin center of 1 resulted in a new six‐coordinate Sn(IV) compound 2 containing two Sn–S bonds. The reaction of 1 with Fe2(CO)9 led to the formation of a stable tin(II) adduct 3 – RAPSn‐Fe(CO)4. The interaction between 1 and [(η5‐C5H5)Fe(CO)2]2 resulted in a transformation of the ligand skeleton. During this reaction, the tin center is oxidized to the tetravalent state, and the donor ═N–CH2–Py group is converted into an anionic one with the loss of the methylene hydrogen atom. The molecular structures of all obtained compounds were determined by single‐crystal X‐ray diffraction. The novel stannylene 1 demonstrates striking activity in benzaldehydes' hydroboration reactions down to 0.02 mole percent of the catalyst loading under mild conditions.
A series of complexes of metal halides with unreduced quinone-type ligands have been synthesized and characterized in detail. The 3,6-di-tert-butyl-obenzoquinone (1) and 4,6-di-tert-butyl-N-aryl-substituted o-iminobenzoquinones (2−5) (aryl is 2,6-dimethylphenyl in 2, 2-methyl-6-ethylphenyl in 3, 2,6-diethylphenyl in 4, and 2,6-diisopropylphenyl in 5) were used to obtain the molecular complexes with metal 12 group halides as well as with indium(III) iodide. The molecular structures of five complexes, bearing an unreduced form of redox-active ligand, have been established by single-crystal X-ray analysis. The spectral data, electrochemical measurements, and DFT calculations indicate the significant transformations of the molecular orbitals of 1−5 upon complexation with Lewis acids. The reduction potentials of o-(imino)quinones in complexes with metal halides shift into the anodic region versus uncoordinated ones. The choice of metal halide allows varying the shift magnitude up to 1.7 V in 2•CdI 2 . The change of the oxidizing ability of the 1−5 upon coordination with Lewis acids enables the oxidation of mercury and ferrocene, infeasible for free ligands.
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