The novel hydrogen-rich binuclear cobalt complex anion, [(CoH3)2H3]5−

Linn, Donald E.; Kieser, Jerod M.; Shearer, Jason

doi:10.1039/c3dt53117a

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Bulky Alkylcyclopentadienyliron Complexes1

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2015

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“…The following analysis of the results of DFT calculations on this compound will confirm that the cobalt atoms of 5 can be regarded as Co(III). The distances to the bridging hydrido ligand Co–H are calculated to be 1.619 and 1.622 Å and are in accord with related hydride bridges reported in the literature. − …”

Section: Bulky Alkylcyclopentadienyliron Complexessupporting

confidence: 85%

Benzylidyne Bridges from Diphenylacetylene and a Methylidyne Bridge from Methylmagnesium Chloride

et al. 2015

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Preparation of the dimeric starting compound [(C5H2 tBu3-1,2,4)Fe(μ-Br)]2 (1) gave a small amount of its green sodium bromide adduct [(C5H2 tBu3-1,2,4)Fe(μ-Br)2Na(DME)2] (2). Reduction of 1 under argon in the presence of diphenylacetylene yielded dark red [(C5H2 tBu3-1,2,4)Fe(μ-CPh)]2 (3) containing two bridging benzylidyne ligands resulting from diphenylacetylene scission. The dicobalt methylidyne complex [{(C5HiPr4)Co}2(μ-CH)(μ-H)] (5) was obtained in high yield from the reaction of [(C5HiPr4)Co(μ-Cl)]2 (4) with two equivalents of methylmagnesium chloride. According to DFT calculations the dinuclear alkylidyne complexes 3 and 5 contain d6 metal centers, namely, iron(II) (3) and cobalt(III) (5). Whereas the benzylidyne ligands of the iron complex 3 display an empty orbital of p z character at the bridging carbon atom, the p z orbital of the methylidyne carbon in the dicobalt complex 5 is filled with a lone pair of electrons.

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