One-dimensional polymers based on [{CpMo(CO)2}2(mu,eta2-P2)]: solid-state conformation analysis by NMR spectroscopy and DFT calculations.

Reaction of the complex [{CpMo(CO)2}2(mu,eta2-P2)] (1) with CuI halides leads to the quantitative formation of the novel one-dimensional linear polymers [CuX{Cp2Mo2(CO)4(mu,eta2:eta1:eta1-P2)}](infinity) (X=Cl (4), Br (5), I (6)). The same products 4 and 5 were obtained when 1 was treated with CuCl2 and CuBr2, 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{Cp2Cr2(CO)4(mu,eta(2):eta1:eta1-P2)}2}3] (X=Cl (4 a), Br (5 a)) in which the molybdenum atoms are replaced by their lighter homologue chromium.