Reactivity of [(2-Phosphino)ethenyl]zirconocene Chloride toward CpM(CO)₃Cl (M = Mo, W): Formation of [(3-Phosphino)propenoyl]dicarbonyl(cyclopentadienyl)metal, {CpM(CO)₂[(CO)CR═CRPPh₂]}

Abstract

Reaction of [(2-phosphino)ethenyl]zirconocene chloride (1) with CpM(CO)3Cl (M = Mo, W) in THF yielded the [(3-phosphino)propenoyl]dicarbonyl(cyclopentadienyl)metals {CpM(CO)2[(CO)CRCRPPh2]} (2). When the reaction between [(2-phosphino)ethenyl]zirconocene chloride (1) and CpMo(CO)3Cl was carried out in the presence of a catalytic amount of Pd(CH3CN)2Cl2, [(3-phosphino)propenoyl]dicarbonyl(cyclopentadienyl)molybdenum, {CpMo(CO)2[(CO)CRCRPPh2]}, was exclusively observed. When [(2-phosphino)ethenyl]zirconocene chloride (1) and MeCpW(CO)3Cl were reacted in the presence of a catalytic amount of CuCl, [(3-phosphino)propenoyl]dicarbonyl(methylcyclopentadienyl)tungsten, {MeCpW(CO)2[(CO)CRCRPPh2]}, was formed. Their structures are determined by X-ray diffraction analysis.

Crystal structures of phosphine-supported (η5-cyclopentadienyl)molybdenum(II) propionyl complexes

“…The current version of the Cambridge Structural Database (Version 5.41, updated August 2020; Groom et al, 2016) has fourteen entries corresponding to molybdenum acyl complexes of the general form Mo(C 5 H 5 )(CO) 2 (PR 3 )(COR). The trans-dicarbonyl structure, as observed for ( 1)-( 3), is preferred except in cases where the phosphine and acyl ligands are covalently linked, forcing them to be cis (Adams et al, 1991;Mercier et al, 1993;Yan et al, 2009).…”

Crystal structures of trans-acetyldicarbonyl(η5-cyclopentadienyl)(1,3,5-triaza-7-phosphaadamantane)molybdenum(II) and trans-acetyldicarbonyl(η5-cyclopentadienyl)(3,7-diacetyl-1,3,7-triaza-5-phosphabicyclo[3.3.1]nonane)molybdenum(II)

“…The current version of the Cambridge Structural Database (Version 5.40, updated August 2019; Groom et al, 2016) has thirteen entries corresponding to molybdenum acyl complexes of the general form Mo(C 5 H 5 )(CO) 2 (PR 3 )(COR). The transdicarbonyl structure, as observed for (1) and (2), is preferred except in cases where the phosphine and acyl ligands are covalently linked, forcing them to be cis (Adams et al, 1991;Mercier et al, 1993;Yan et al, 2009). The PTA and DAPTA ligands have not been extensively utilized on molybdenum.…”

Crystal structures oftrans-acetyldicarbonyl(η5-cyclopentadienyl)(dimethylphenylphosphane)molybdenum(II) andtrans-acetyldicarbonyl(η5-cyclopentadienyl)(ethyldiphenylphosphane)molybdenum(II)

“…ligands are covalently linked, forcing them to be cis (Adams et al, 1991;Mercier et al, 1993;Yan et al, 2009). The preference for a trans geometry is likely at least partly steric in nature, since the only example with a cis-dicarbonyl geometry without linked phosphine and acyl ligands is for a molybdenum formyl with a small trimethylphosphine ligand and a bulky pentamethylcyclopentadienyl ligand (Asdar et al, 1989).…”