[PPN][Fe₃(CO)₉(C⋮CH)] and [Fe₃(CO)₉(C⋮COTi(THF)₄Cl)] from the Reaction of Low-Valent Titanium with [Fe₃(CO)₉(CCO)]^2-

Abstract

TiCl3(DME)1.5 (DME = 1,2-dimethoxyethane) and a Zn−Cu couple react with [PPN]2[Fe3(CO)9(CCO)] to give the new compound [PPN][Fe3(CO)9(C⋮CH)] (I) (70% yield), a known compound [Fe3(CO)10(CCH2)] (II) (9% yield), and another new compound [Fe3(CO)9(CCOTi(THF)4Cl)] (III). Compound I was characterized by 1H and 13C NMR, IR, mass spectrometry, and X-ray crystallography. Compound III was characterized by IR, mass spectrometry, 13C NMR, and X-ray crystallography.

Formation of a μ3-Acetylide on a Ru3 Cluster via Coupling of μ-Methylene with Isocyanide Accompanied by Elimination of Amine: A Model of Hydrogen-Assisted C–C Bond Formation on a Metal Surface

“…Formation of the μ 3 -ethynyl ligand was confirmed by the 13 C NMR signals at δ 188.1 (s) and 116.1 (d, J CH = 209 Hz), which were assigned to the α- and β-carbons of the ethynyl ligand, respectively. The large J CH value of the β-carbon was comparable to those in [(Cp*Fe)­Ru 2 (μ 3 -CCH)­(CO) 4 (μ-CO)­(μ-dppm)] (dppm = bis­(diphenylphosphino)­methane) (δ β 111.2 (d, J CH = 215 Hz)) and in [Fe 3 (μ 3 -CCH)­(CO) 9 ] − (δ β 154.5 (d, J CH = 188 Hz)) …”