Novel Group 4, 9, 10, and 12 Complexes of Indenyl-Derived Ylides

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Purdavaie, Kourosh
phosphonium-1-indenylide (PHIN) , Organometallic , Inorganic
The coordination chemistry of the phosphonium-1-indenylide (PHIN) ligand methyldiphenylphosphonium-1-indenylide (1-C9H6PMePh2, I) has been studied, and a new phosphonium-1-indenylide (PHIN) ligand methyldiphenylphosphonium-4,7-dimethyl-1-indenylide (4,7-dimethyl-1-C9H4PMePh2, II) has prepared and characterized by NMR spectroscopy, elemental analysis and X-ray crystallography. The zwitterionic structure of methyldiphenylphosphonium-4,7-dimethyl-1-indenylide II is isoelectronic with the cyclopentadienyl ligand and one can anticipate interesting coordination chemistry.[Ir(COD)][BF4] and [Rh(COD)][BF4] were prepared by reactions of silver tetrafluoroborate, AgBF4, with [Ir(COD)Cl]2 and [Rh(COD)Cl]2 and by reacting the resulting [Ir(COD)][BF4] and [Rh(COD)][BF4] with I and II. The resulting planar chiral iridium(I) and rhodium(I) complexes [Ir(η4-C8H12)(η5-I)]BF4 (III), [Ir(η4-C8H12)(η5-II)]BF4 (IV), [Rh(η4-C8H12)(η5-I)]BF4 (V), and [Rh(η4-C8H12)(η5-II)]BF4 (VI) were synthesized as pairs of enantiomers depending on which face of five-membered rings coordinates to the metal centers. The iridium and rhodium complexes have been characterized by extensive NMR spectroscopy, high resolution mass spectrometry and elemental analyses. Hydrogenation of [Rh(η4-C8H12)(η5-I)]BF4 (V) and the oxidative addition of methyl iodide and benzyl chloride to all the new complexes III-VI were attempted. Coordination of I to a variety of metals in Groups IV, IX, X, and XII, was attempted.
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