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(Ether‐phosphane)iron(II) Complexes with the Coordination Numbers Four, Five, and Six Photolysis of cis,cis,trans1‐Br2(OC)2 Fe(P∑O)2 (1a, b) [O,PPh2PCH2CH2OCH3 (a), Ph2PCH2C4H7O (b)] results in the formation of the iron(II) complexes Br2Fe(P∼O)2 (2a), [BrFe‐(P∩O)(μ1‐Br)]2 (4b), and [trans1‐Br2Fe(P∩O)(μ1‐CO)]2 (5a) with the coordination numbers four, five, and six, respectively. 2a crystallizes in the triclinic space group P\documentclass{article}\pagestyle{empty}\begin{document}$\bar{1}$\end{document} with Z2 and has two monodentated O,P functions (P∼O: η1‐P1‐coordinated; P∩O:η2‐O,P1‐coordinated). The dimeric complex 4b with two O∩P‐chelated ligands crystallizes in the orthorhombic space group Pbca with Z4. 2a and 4b, which react under CO pressure to give the starting complexes 1a, b, are also accessible from the ether‐phosphanes 3a, b and anhydrous FeBr2.