One‐Dimensional Polymers Based on [{CpMo(CO) 2 } 2 (μ,η 2 ‐P 2 )]: Solid‐State Conformation Analysis by NMR Spectroscopy and DFT Calculations

Reaction of the complex [{CpMo(CO) 2 } 2 (μ,η 2 ‐P 2 )] ( 1 ) with Cu I halides leads to the quantitative formation of the novel one‐dimensional linear polymers [CuX{Cp 2 Mo 2 (CO) 4 (μ,η 2 :η 1 :η 1 ‐P 2 )}] ∞ (X=Cl ( 4 ), Br ( 5 ), I ( 6 )). The same products 4 and 5 were obtained when 1 was treated with CuCl 2 and CuBr 2 , respectively. The solid‐state structures are compared and their remarkable influence on the respective 31 P magic angle spinning (MAS) NMR spectra is interpreted with the help of density functional theory (DFT) calculations on the model compounds [{(CuX) 2 {Cp 2 Cr 2 (CO) 4 (μ,η 2 :η 1 :η 1 ‐P 2 )} 2 } 3 ] (X=Cl ( 4 a ), Br ( 5 a )) in which the molybdenum atoms are replaced by their lighter homologue chromium.