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One‐Dimensional Polymers Based on [{CpMo(CO) 2 } 2 (μ,η 2 ‐P 2 )]: Solid‐State Conformation Analysis by NMR Spectroscopy and DFT Calculations
Author(s) -
Scheer Manfred,
Gregoriades Laurence,
Bai Junfeng,
Sierka Marek,
Brunklaus Gunther,
Eckert Hellmut
Publication year - 2005
Publication title -
chemistry – a european journal
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 1.687
H-Index - 242
eISSN - 1521-3765
pISSN - 0947-6539
DOI - 10.1002/chem.200401117
Subject(s) - density functional theory , chemistry , magic angle spinning , molybdenum , crystallography , nuclear magnetic resonance spectroscopy , spectroscopy , halide , polymer , solid state nuclear magnetic resonance , solid state , stereochemistry , computational chemistry , inorganic chemistry , nuclear magnetic resonance , physics , organic chemistry , quantum mechanics
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.