No abstract

Reduction of [CpFe(μ-Br)] (1, Cp = C(CH-4-Et)) by potassium napthalenide, followed by the addition of white phosphorus, affords [K(18-c-6){CpFe(η-P)}] (2, 18-c-6 = [18]crown-6), which features a planar cyclo-P ligand. The related diiron complex [Na(THF)(CpFe)(μ,η-P)] (3) was obtained by reducing 1 with sodium amalgam in the presence of P. Protonation of 3 affords [Na(THF)][(CpFe)(μ,η-P)(H)] (4), while the reaction of 3 with trimethylchlorosilane gives the nortricyclane compound P(SiMe) as the main product.

Oxidative addition of the P‒P single bond of an ortho-carborane-derived 1,2-diphosphetane (1,2-C2(PMes)2B10H10) (Mes = 2,4,6-Me3C6H2) to cobalt(-I) and nickel(0) sources affords the first heteroleptic complexes of a carborane-bridged bis(phosphanido) ligand....

New iron complexes [Cp*FeL]− (1‐σ and 1‐π, Cp*=C5Me5) containing the chelating phosphinine ligand 2‐(2′‐pyridyl)‐4,6‐diphenylphosphinine (L) have been prepared, and found to undergo facile reaction with CO2 under ambient conditions. The outcome of this reaction depends on the coordination mode of the versatile ligand L. Interaction of CO2 with the isomer 1‐π, in which L binds to Fe through the phosphinine moiety in an η5 fashion, leads to the formation of 3‐π, in which CO2 has undergone electrophilic addition to the phosphinine group. In contrast, interaction with 1‐σ—in which L acts as a σ‐chelating [P,N] ligand—leads to product 3‐σ in which one C=O bond has been completely broken. Such CO2 cleavage reactions are extremely rare for late 3d metals, and this represents the first such example mediated by a single Fe centre.