In this contribution we report the synthesis of the novel unsymmetrical ferrocene‐based pincer‐type proligand η5‐CpFeη5‐C5H2‐1‐Br‐2‐PPh2‐5‐CH2NMe2 (1). Its reactivity is demonstrated by isolation of related organotin derivatives η5‐CpFeη5‐C5H2‐1‐SnR3‐2‐PPh2‐5‐CH2NMe2 (3, R = Ph; 4, R = Me). The reactions of compounds 3 and 4 with H2O2 and elemental sulfur gave the corresponding ferrocenylphosphane oxide (5) and the sulfides (6, 7), respectively. Most remarkably, an unprecedented reaction of the organotin derivative 3 with elemental iodine was observed, providing the ammonium salt [η5‐CpFeη5‐C5H2‐1‐SnPh2I‐2‐P(O)Ph2‐5‐CH2NHMe2]I (8). The compounds are characterized by elemental analyses, 1H, 13C, 31P, 119Sn NMR spectroscopy, electrospray ionization mass spectrometry, and single‐crystal X‐ray diffraction analyses (3–8). Also reported are the solid‐state structures of the hydrolysis products [η5‐CpFeη5‐C5H2‐1‐SnPh2(OH)‐2‐P(O)Ph2‐5‐CH2NHMe2]·0.5H2O (9a) and [η5‐CpFeη5‐C5H2‐1‐SnPh(OH)‐2‐P(O)Ph2‐5‐CH2NMe2]2[I3]2 (9b) that were isolated by serendipity.

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The reaction of sodium chloride with 2-[bis(2-hydroxyethyl)amino]ethan-1-ol results in the formation of the title salt {[Na{N(CH2CH2OH)3}]Cl} n . The polymeric structure is characterized by a sodium cation coordinated by one nitrogen and five oxygen atoms in a distorted octahedral environment. The resulting one-dimensional {—O—Na—O—Na—O}— coordination polymer extends parallel to [010] and is connected through the chloride counter-anion via O—H...Cl hydrogen bonding, giving rise to a two-dimensional supramolecular structure parallel to (001).