Conformational Analysis of One‐Dimensional Coordination Polymers Based on [Cp 2 Cr 2 (CO) 4 (μ,η 2 ‐P 2 )] by Solid‐State Multinuclear NMR Spectroscopy and Density Functional Calculations

Reaction of the complex [Cp 2 Cr 2 (CO) 4 (μ,η 2 ‐P 2 )] ( 2 ) with copper(I) halides leads to the quantitative formation of the new one‐dimensional (1D) linear polymers [CuX{Cp 2 Cr 2 (CO) 4 (μ,η 2 :η 1 :η 1 ‐P 2 )}] n [X = Cl ( 3 ), Br ( 4 ), I ( 5 )]. Polymers 3 – 5 are the first examples of supramolecular aggregates incorporating 2 as a connecting moiety. The solid‐state structures of 3 – 5 are compared and their remarkable influence on the respective solid‐state 31 P magic angle spinning (MAS) NMR spectra is interpreted with the help of density functional theory (DFT) calculations, which suggest that the 31 P chemical shifts are extremely sensitive to the position of the phosphorus atoms with respect to the cones of anisotropy of the carbonyl ligands. (© Wiley‐VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany, 2007)