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The analysis of the 63Cu and 31PNMR resonances and the spin-spin coupling patterns for elucidation of the Cu(I) phosphines complexes geometry and ligands' coordination modes in solutions are reviewed. The influences of the steric and electronic properties of P-donor ligands and the dynamic processes in solution on the 63Cu and 31P NMR spectra of Cu(I) complexes are discussed.
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