503153-03-5Relevant academic research and scientific papers
Reactions of ring-slipped iron complexes derived from P(=S)Ph-bridged [1]ferrocenophane: Synthesis of bis(half-sandwich) heterodinuclear complexes
Imamura, Yuki,Kubo, Kazuyuki,Mizuta, Tsutomu,Miyoshi, Katsuhiko
, p. 2301 - 2307 (2006)
P(=S)Ph-bridged [1]ferrocenophane, [Fe{(η5-C 5H4)2P(=S)Ph}] (1), reacted under UV-vis photoirradiation with P(OMe)3, P(OMe)2Ph, or PMe 3 to give respective ring-slipped products. The reaction with P(OMe)3 afforded [Fe{(η5-C5H 4)(η1-C5H4)P(=S)Ph}{P(OMe) 3}2] (2a), while the bulkier P(OMe)2Ph gave initially the similar complex 2b, but gradual dissociation of the η1-C5H4 moiety took place from the iron center in THF to form [Fe{η5-C5H4P(=S) Ph(C5H4)-KS}{P(OMe)2Ph}2] (4b), in which the η5-C5H4 ring bearing a P=S pendant group adopted an unprecedented η5-kS coordination mode and the other C5H4 group left the coordination sphere of the iron atom. The reaction with PMe3 gave directly the corresponding η5-kS product 4c in ether, but its P=S group was replaced in THF with the remaining PMe3 to give [Fe{(η5-C 5H4)P(=S)Ph(C5H4)}(PMe 3)3] (3c) with the P(=S)Ph(C5H4) group dangling from the η5-C5H4 ring. When 2a having an η1-C5H4 group was allowed to react with [M(CO)3(NCMe)3] (M = Mo, W), the iron-molybdenum and -tungsten heterodinuclear complexes {μ-η5: η5-(C5H4)2P(=S)Ph-kS}[Fe{P(OMe) 3}2]-[M(CO)3] (M = Mo (5-Mo), W (5-W)) were obtained, in which the two metal fragments were linked with an η5-C5H4P(=S)Ph(η5-C 5H4)-kS bridge. In addition, 5-Mo and 5-W were readily converted in acetonitrile to the respective acetonitrile complexes {μ-η5:η5-(C5H4) 2P(=S)Ph}[Fe(NCMe){P(OMe)3}2]-[M(CO) 3], with the P=S group giving up coordination to the iron center. A variety of these reaction patterns observed were discussed in terms of steric bulkiness and basicity of the phosphorus ligands concerned.
