Organometallics p. 2724 - 2728 (1989)
Update date:2022-07-29
Topics:
Coan, Paul S.
Folting, Kirsten
Huffman, John C.
Caulton, Kenneth G.
The structure and the solution behavior of the compounds MeCuLn (Ln = (PPh3)3, (PMePh2)3, and (Ph2PCH2)3CMe) have been characterized by variable-temperature 1H and 31P NMR studies and (for PPh3) X-ray diffraction. All three compounds exist as monomeric, four-coordinate, 18-electron species at low temperatures in noncoordinating solvents, but ligand dissociation is already evident for PPh3 and PMePh2 at -80°C. The PPh3 complex, which crystallizes from THF/pentane as MeCu(PPh3)3·THF (THF is in the crystal lattice and does not coordinate to copper), is shown by X-ray diffraction to have a nearly tetrahedral structure with Cu-C = 2.043 (12) and Cu-P = 2.313 (3) A?. The crowded intramolecular packing of phenyl groups is evident from the X-ray study, which then rationalizes the tendency of this complex to dissociate PPh3. The thermal decomposition of MeCu(PPh3)3 in solution is indicated to proceed via unsaturated MeCu(PPh3)2. Crystallographic data for MeCu(PPh3)3·THF (at -154°C): space group P21 with a = 13.153 (5) A?, b = 10.125 (3) A?, c = 18.083 (7) A?, β = 93.19 (2)°, and Z = 2.
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