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A cluster‐ligand is disclosed in the form of [Ru3(CN)3(CO)9]3− ([1]3−). Produced by simple reaction of [Ru3(CO)12] with cyanide, [1]3− serves as a precursor to a series of μ‐CN cages. When treated with [Ru3(CO)12], it readily forms the prism [Ru6(μ‐CN)3(CO)18]3−. With 1.5 equiv. of [Cu(MeCN)4]+ [1]3− reacts to give the expanded prism {Cu3[Ru3(μ‐CN)3(CO)9]2}3−, which features three two‐coordinate Cu(I) centers. Sources of Ni2+ and Fe2+ bind two equivalents of [1]3−, giving the double cages {M[Ru3(μ‐CN)3(CO)9]2}4− (M=Ni, Fe) wherein the central metal is octahedral. The 1 : 1 reaction using [Fe(H2O)6]2+ gave the interpenetrated super‐tetrahedrane {Fe4(μ4‐O)[Ru3(μ‐CN)3(CO)9]4}4−. [ABSTRACT FROM AUTHOR]

The paper aims to elucidate the final stages in the biosynthesis of the [2Fe] H active site of the [FeFe]-hydrogenases. The recently hypothesized intermediate [Fe 2 (SCH 2 NH 2 ) 2 (CN) 2 (CO) 4 ] 2- ([1] 2- ) was prepared by a multistep route from [Fe 2 (S 2 )(CN)(CO) 5 ] - . The following synthetic intermediates were characterized in order: [Fe 2 (SCH 2 NHFmoc) 2 (CNBEt 3 )(CO) 5 ] - , [Fe 2 (SCH 2 NHFmoc) 2 (CN)-(CO) 5 ] - , and [Fe 2 (SCH 2 NHFmoc) 2 (CN) 2 (CO) 4 ] 2- , where Fmoc is fluorenylmethoxycarbonyl). Derivatives of these anions include [K(18-crown-6)] + , PPh 4 + and PPN + salts as well as the 13 CD 2 -isotopologues. These Fe 2 species exist as a mixture of two isomers attributed to diequatorial (ee) and axial-equatorial (ae) stereochemistry at sulfur. In vitro experiments demonstrate that [1] 2- maturates HydA1 in the presence of HydF and a cocktail of reagents. HydA1 can also be maturated using a highly simplified cocktail, omitting HydF and other proteins. This result is consistent with HydA1 participating in the maturation process and refines the roles of HydF., (© 2024 The Authors. Angewandte Chemie International Edition published by Wiley-VCH GmbH.)

A cluster-ligand is disclosed in the form of [Ru 3 (CN) 3 (CO) 9 ] 3- ([ 1 ] 3- ). Produced by simple reaction of [Ru 3 (CO) 12 ] with cyanide, [ 1 ] 3- serves as a precursor to a series of μ-CN cages. When treated with [Ru 3 (CO) 12 ], it readily forms the prism [Ru 6 (μ-CN) 3 (CO) 18 ] 3- . With 1.5 equiv of [Cu(MeCN) 4 ] + [ 1 ] 3- reacts to give the expanded prism {Cu 3 [Ru 3 (μ-CN) 3 (CO) 9 ] 2 } 3- , which features three two-coordinate Cu(I) centers. Sources of Ni 2+ and Fe 2+ bind two equivalents of [ 1 ] 3- , giving the double cages {M[Ru 3 (μ-CN) 3 (CO) 9 ] 2 } 4- (M = Ni, Fe) wherein the central metal is octahedral. The 1:1 reaction using [Fe(H 2 O) 6 ] 2+ gave the interpenetrated super-tetrahedrane {Fe 4 (μ 4 -O)[Ru 3 (μ-CN) 3 (CO) 9 ] 4 } 4- ., Competing Interests: Conflicts of interest There are no conflicts to declare.