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Sünkel, Karlheinz and Klein-Hessling, Christian (2021): Crystal and molecular structures of some phosphane-substituted cymantrenes [(C5H4X)Mn(CO)LL '] (X= H or CI, L' =CO,L '= PPh3 or PCy3, and LL ' Ph2PCH2CH2PPh2). In: Acta Crystallographica Section C-Structural Chemistry, Vol. 77: 633-

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UV irradiation of tetrahydrofuran solutions of [CpMn(CO)(3)] (Cp = pi-C5H5 or pi-C5H4Cl) in the presence of the phosphanes PPh3 or PCy3 (Cy = cyclohexyl) and Ph2PCH2CH2PPh2 yields the substitution products [CpMn(CO)(2)PR3] (R = Ph or Cy) and [CpMn(CO)(Ph2PCH2CH2PPh2)], namely, dicarbonyl(eta(5)-cyclopentadienyl)(triphenylphosphane-KP)manganese(I), [Mn(C5H5)(C18H15P)(CO)(2)], 1a, dicarbonyl (eta(5)-1 -chlorocyclopentadienyl) (triphenylphosphane-kappa P)mang anese (I), [Mn(C5H4Cl) (C18H15P) (CO)(2)], 1b, dicarbonyl(eta(5)-cyclopentadienyl) (tricyclohexylphosphane-kappa P) manganese (I), [Mn(C5H5) (C18H33P)(CO)(2)], 2a, dicarbonyl(eta(5)-1-chlorocyclopentadienyl)(tricyclohexylphosphane-KP)manganese(I), [Mn(C5H4Cl) (C18H33P) (CO)(2)], 2b, carbonyl(q 5 -cyclopentadienyl)[1,2-bis(diphenylphosphanyl)ethane-kappa(2) P,P']manganese(I), [Mn(C5H5)(C26H24P2)(CO)], 3a, and carbonyl(q 5 -1-chlorocyclopentaclieny1)[1,2-bis(cliphenylphosphanyl)ethane-kappa P-2,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 PR 3 groups avoid being eclipsed with the C-Cl bonds. All the compounds employ weak C-H center dot center dot center dot O interactions for intermolecular association, which are enhanced by C-H center dot center dot center dot Cl contacts in the chlorinated products.

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