Synthesis and Structure of a New Type of Chiral Organoiron and Organoruthenium Complexes

Abstract

~~The synthesis of 36 [Fe(C0)2L1(q4-diene)], three [Fe(CO)2L'(q4-enone)], and five [Ru(CO),L'(q4-diene)] complexes (L' = Ph,P, Et,P, (EtO),P, (MeO),P, C6HIINC) by thermal, selective CO ligand displacement in the corresponding tricarbonyl precursor complexes is described. In a second step, photochemical CO displacement by another phosphorus ligand L2 leads to a new type of q4-diene complexes with a centre of chirality at the metal atom (Fe, Ru). 23 Fe and three Ru complexes of this type have been prepared and characterized. In the case ofcomplexes with unsymmetrical dienes, racemic diastereoisomers are formed which can be separated by chromatographic methods. The molecular structures of [Fe(CO)(Ph3P)((MeO),P)(buta-l,3-diene)] (52), [Fe(CO)(Ph,P)((MeO),P) (isoprene)] (58) and [Fe(CO)(Et,P)(EtO),P)(hexa-2,4-dienal)] (62a) were determined by X-ray diffraction. AllComplexes were investigated by I3C-, ,'P-and, in part, 'H-NMR spectroscopy. At low temperatures, conformational isomers (rotamers) can be differentiated which probably arise from v/ rotation at the coordinated metal centre.

New Applications of N-Acyliminium Precursors: Tetracarbonyliron-Mediated Stereoselective Alkylations of 5-(R)-Isopropoxy-3-pyrrolin-2-ones

“…[28] The substitution of a carbonyl ligand in cis-9 for a worse π-When the tricarbonyliron complex 32 was treated with acceptor, such as a phosphane or a phosphite, would render triphenylphosphane the yellow complex 33, in which the the complex 30 more electron-rich. [28] The substitution of a carbonyl ligand in cis-9 for a worse π-When the tricarbonyliron complex 32 was treated with acceptor, such as a phosphane or a phosphite, would render triphenylphosphane the yellow complex 33, in which the the complex 30 more electron-rich.…”

A New Phosphinite Chelate, (aryl)2POBF2OH, Complexed to Ruthenium(II). HBF4-Induced P−C Bond Cleavage in Chiral MeO-Biphep Complexes

“…(iv) In both the 1 H and 13 C spectra one observes four relatively low frequency absorptions, due to the four CH types in the η 6 -arene moiety. For 3a these four carbon signals, C3−C6, appear at 78.6, 95.4, 101.7, and 76.0 ppm, respectively, exactly where one expects 13 C resonances of arenes complexed to Ru(II). −

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Synthesis and NMR Spectroscopic Characterization of Organometallics in the Laboratory of Wolfgang von Philipsborn: Reminiscences of Former Graduate Students

“…His synthetic work was mainly concerned with organometallic chemistry (e.g. [1] ), often in collaboration with his colleagues in inorganic chemistry at the University, e.g. Albrecht Salzer or Heinz Berke, or from the ETH, e.g.…”