Crystal and molecular structures of some phosphane‐substituted cymantrenes [(C5H4X)Mn(CO)LL′] (X = H or Cl, L = CO, L′ = PPh3 or PCy3, and LL' = Ph2PCH2CH2PPh2)

• Published in: Acta crystallographica. Section C, Crystal structure communications Vol. 77; no. 10; pp. 633 - 640
• Main Authors: Sünkel, Karlheinz, Klein-Hessling, Christian
• Format: Journal Article
• Language: English
• Published: 5 Abbey Square, Chester, Cheshire CH1 2HU, England International Union of Crystallography 01.10.2021; Wiley Subscription Services, Inc
• Subjects: Bonding strength; Carbon monoxide; Carbonyl compounds; Carbonyls; Chemical bonds; Chlorine; Crystal structure; Crystals; cymantrene; Ethane; Irradiation; Manganese; Molecular structure; phosphane complexes; Substitutes; Tetrahydrofuran; Ultraviolet radiation; weak interactions; weak interactions; crystal structure; cymantrene; phosphane complexes; irradiation
• ISSN: 2053-2296; 0108-2701; 2053-2296; 1600-5759
• DOI: 10.1107/S2053229621009177

UV irradiation of tetrahydrofuran solutions of [CpMn(CO)3] (Cp = π‐C5H5 or π‐C5H4Cl) in the presence of the phosphanes PPh3 or PCy3 (Cy = cyclohexyl) and Ph2PCH2CH2PPh2 yields the substitution products [CpMn(CO)2PR3] (R = Ph or Cy) and [CpMn(CO)(Ph2PCH2CH2PPh2)], namely, dicarbonyl(η5‐cyclopentadienyl)(triphenylphosphane‐κP)manganese(I), [Mn(C5H5)(C18H15P)(CO)2], 1a, dicarbonyl(η5‐1‐chlorocyclopentadienyl)(triphenylphosphane‐κP)manganese(I), [Mn(C5H4Cl)(C18H15P)(CO)2], 1b, dicarbonyl(η5‐cyclopentadienyl)(tricyclohexylphosphane‐κP)manganese(I), [Mn(C5H5)(C18H33P)(CO)2], 2a, dicarbonyl(η5‐1‐chlorocyclopentadienyl)(tricyclohexylphosphane‐κP)manganese(I), [Mn(C5H4Cl)(C18H33P)(CO)2], 2b, carbonyl(η5‐cyclopentadienyl)[1,2‐bis(diphenylphosphanyl)ethane‐κ2P,P′]manganese(I), [Mn(C5H5)(C26H24P2)(CO)], 3a, and carbonyl(η5‐1‐chlorocyclopentadienyl)[1,2‐bis(diphenylphosphanyl)ethane‐κ2P,P′]manganese(I), [Mn(C5H4Cl)(C26H24P2)(CO)], 3b, The crystal structure determinations show a very small influence of the chlorine substitution and a moderate influence of the phosphane substitution on the bond lengths. The PR3 groups avoid being eclipsed with the C—Cl bonds. All the compounds employ weak C—H…O interactions for intermolecular association, which are enhanced by C—H…Cl contacts in the chlorinated products. The syntheses and structures of the cymantrenes [(C5H4X)Mn(CO)LL′] (X = H or Cl; L = CO: L′ = PPh3 or PCy3; LL′ = Ph2PCH2CH2PPh2) are reported. Substitution of CO by phosphanes influences the bond parameters more than replacing the C5H5 ligand by C5H4Cl.