Abstract
The reaction of [Cp*Fe(eta(5)-As-5)] (1) with Cu-I halides leads to the formation of the 1D-polymeric compounds [{Cu(mu-X)}(3)(CH3CN){Cp*Fe(eta(5):eta(2):eta(2):eta(2)-As-5)}](n) (X = Cl (2), Br (3)), [{Cu(mu(3)-I)}(2){Cp*Fe(eta(5):eta(2):eta(2)-As-5)}](n) (4) and [{Cu(mu-I)}(3){CuI}{Cp*Fe(eta(5):eta(2):eta(2):eta(1):eta(1)-As-5)}{Cp*Fe(eta(5):eta(5):eta(2)-As-5)}](n) (5). The polymers are built ...
Abstract
The reaction of [Cp*Fe(eta(5)-As-5)] (1) with Cu-I halides leads to the formation of the 1D-polymeric compounds [{Cu(mu-X)}(3)(CH3CN){Cp*Fe(eta(5):eta(2):eta(2):eta(2)-As-5)}](n) (X = Cl (2), Br (3)), [{Cu(mu(3)-I)}(2){Cp*Fe(eta(5):eta(2):eta(2)-As-5)}](n) (4) and [{Cu(mu-I)}(3){CuI}{Cp*Fe(eta(5):eta(2):eta(2):eta(1):eta(1)-As-5)}{Cp*Fe(eta(5):eta(5):eta(2)-As-5)}](n) (5). The polymers are built up by the pi-coordination of the cyclo-As-5 ring to (CuX)(n) moieties forming discrete units, which are additionally linked by weak intermolecular As center dot center dot center dot Cu sigma-interactions. Only polymer 4 is an exception revealing a (CuI)(n) ladder which is alternately coordinated by molecules of 1. In a side arm of polymer 5 a novel eta(5)-coordination of a Cu atom below the cyclo-As-5 ring is found, showing an unprecedented heteroleptic triple-decker sandwich complex with a polyarsenic middle-deck. All products are characterised by single crystal X-ray structure analysis. To define the differences in the coordination behaviour of 1 and its phosphorus analogue [Cp*Fe(eta(5)-P-5)] (1a), DFT calculations are described.
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