Lewis-base adducts of Group 11 metal(I) compounds. Part 28. Solid-state phosphorus-31 cross-polarization magic-angle spinning nuclear magnetic resonance and structural studies on the mononuclear 3: 1 adducts of triphenylphosphine with copper(I) halides

摘要: Solid-state cross-polarization magic-angle spinning 31P n.m.r. data and single-crystal X-ray diffraction structure determinations are reported for solvated unsolvated 3 : 1 adducts of triphenylphosphine with copper(I) halides, [Cu(PPh3)3X]. The structures the bromide iodide complexes isomorphous previously studied chloride analogue, crystallizing in trigonal space group P3 three independent molecules each disposed about a crystallographic three-fold symmetry axis. Two related by pseudo-inversion centre. PPh3 ligands adopt skewed conformation Cu–P respect to Cu–X [X–Cu–P–C(l11) angles 30.6–34.1 °]. distances not halide dependent [Br, 2.351(4), 2.340(4), 2.369(4)A; I, 2.362(3), 2.346(5), 2.357(5)A] all P–Cu–P close tetrahedral value. spectra reveal two symmetric quartets an intensity ratio 2: 1; average chemical shifts overall –10, –13, –17 p.p.m. X = Cl, Br, I respectively. splittings within quartet also ranging between 900 940 Hz. high is assigned enantiomerically molecules. acetone crystallize triclinic P isomorphous. Solvation changes from staggered, X–Cu–P–C(l11) 45.5–56.3°. potential increase back strain because this conformational change relieved ∼ 5° angles. bond lengths again do significantly halogen series. solid-state single shifted downfield 6–10 p.p.m.; slightly more asymmetric than phase splitting values lying range 890–980