New high-spin iron complexes based on bis(imino)acenaphthenes (BIAN): synthesis, structure, and magnetic properties

Fedushkin, Igor L.; Skatova, Alexandra A.; Khvoinova, N. M.; Lukoyanov, Anton N.; Fukin, Georgy K.; Ketkov, Sergey Yu.; Maslov, Maxim O.; Bogomyakov, A. S.; Makarov, V. M.

doi:10.1007/s11172-013-0311-y

Cited by 20 publications

(19 citation statements)

References 26 publications

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“…The twist angle between the two CoN 2 planes is 54.94(7)°. The NCCN bond lengths of BIAN are slightly shorter than in 3 (Figure 1; C−N 1.333 3 36 Accordingly, the observed bond lengths of the BIAN ligands in 4 suggest a radical anion state of BIAN which is supported by theoretical studies (vide infra). 28,29,37 The sum formula of 4a was further verified by negative-ion mode ESI mass spectrometry (Figure 4, m/z = 1121.4).…”

Section: ■ Results and Discussionsupporting

confidence: 65%

Cobalt-Catalyzed Hydrogenations via Olefin Cobaltate and Hydride Intermediates

et al. 2019

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Redox noninnocent ligands are a promising tool to moderate electron transfer processes within base-metal catalysts. This report introduces bis(imino)acenaphthene (BIAN) cobaltate complexes as hydrogenation catalysts. Sterically hindered trisubstituted alkenes, imines, and quinolines underwent clean hydrogenation under mild conditions (2−10 bar, 20−80°C) by use of the stable catalyst precursor [(Dipp BIAN)CoBr 2 ] and the cocatalyst LiEt 3 BH. Mechanistic studies support a homogeneous catalysis pathway involving alkene and hydrido cobaltates as active catalyst species. Furthermore, considerable reaction acceleration by alkali cations and Lewis acids was observed. The dinuclear hydridocobaltate anion with bridging hydride ligands was isolated and fully characterized.

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Section: ■ Results and Discussionsupporting

confidence: 65%

Cobalt-Catalyzed Hydrogenations via Olefin Cobaltate and Hydride Intermediates

et al. 2019

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“…The number of transition‐metal complexes in which the metal is coordinated by three BIAN ligands is quite limited, and most of these examples are best described with at least one ligand being reduced to a radical anion. To our knowledge, [Cr{(3,5‐Xyl) 2 BIAN} 3 ][PF 6 ] 3 and [Fe(H 2 BIAN) 3 ][FeBr 3 (thf)] 2 are the only exceptions.…”

Section: Resultsmentioning

confidence: 99%

Synthesis and Catalysis of Redox‐Active Bis(imino)acenaphthene (BIAN) Iron Complexes

et al. 2017

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Reactions of various substituted bis(imino)acenaphthenes (R‐BIANs) with FeCl2(thf)1.5 afforded the tetrahedral complexes (R‐BIAN)FeCl2 (2) from bulky α‐diimines and the octahedral complexes [Fe(R‐BIAN)3][FeCl4]2 (3) from less bulky ligands. The driving force for the formation of complexes 3 is the high ligand‐field stabilization of the low‐spin FeII center. The two sets of complexes exhibit distinct charge‐transfer band intensities and redox activities. (R‐BIAN)FeCl2 complexes showed reversible ligand‐centered reductions at −0.9 V (vs. FcH/FcH+; FcH: ferrocene); further reduction led to decomposition. Irreversible oxidations were observed at 0.2 and 0.4 V, associated with a reduction at −0.4 V, as well as a ligand‐centered redox event at 1.0 V. First applications of the Fe(BIAN) complexes to hydrogenations of alkenes indicated good catalytic activity under mild conditions.

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“…Note that [FeBr 3 (THF)] – is a well‐known anionic Fe II complex, whose formation from iron(II) bromide in THF solution has been observed in a complexation reaction consuming only part of the Fe II . An additional problem we encountered with 6 is the fact that standard purification of the crude product by anaerobic column chromatography using Celite®, silca gel or alumina failed due to very limited solubility combined with a pronounced tendency to decompose on the stationary phase.…”

Section: Resultsmentioning

confidence: 99%

The Interaction of 1,1′‐Diphosphaferrocenes with Gold: Molecular Coordination Chemistry and Adsorption on Solid Substrates

et al. 2016

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1,1′-Diphosphaferrocene (1) and its 3,3′,4,4′-tetramethyl (2), 3,3′,4,4′-tetraphenyl (3), octamethyl (4), octaethyl (5) and octaphenyl derivative (6) have been investigated in terms of the suitability of 1,1′-diphosphaferrocenes as adsorbate species for fabricating self-assembled monolayers (SAMs) on gold. Compounds 3 and 6 have been structurally characterised by Xray diffraction. Complexes [Au (4)

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New high-spin iron complexes based on bis(imino)acenaphthenes (BIAN): synthesis, structure, and magnetic properties

Cited by 20 publications

References 26 publications

Cobalt-Catalyzed Hydrogenations via Olefin Cobaltate and Hydride Intermediates

Cobalt-Catalyzed Hydrogenations via Olefin Cobaltate and Hydride Intermediates

Synthesis and Catalysis of Redox‐Active Bis(imino)acenaphthene (BIAN) Iron Complexes

The Interaction of 1,1′‐Diphosphaferrocenes with Gold: Molecular Coordination Chemistry and Adsorption on Solid Substrates

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