One-Dimensional Polymers Based on [{CpMo(CO)2}2(μ,η2-P2)]: Solid-State Conformation Analysis by NMR Spectroscopy and DFT Calculations

✍ Scribed by Manfred Scheer; Laurence Gregoriades; Junfeng Bai; Marek Sierka; Gunther Brunklaus; Hellmut Eckert

• Publisher: John Wiley and Sons
• Year: 2005
• Tongue: English
• Weight: 211 KB
• Volume: 11
• Category: Article
• ISSN: 0947-6539
• DOI: 10.1002/chem.200401117

✦ Synopsis

Abstract

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.