Abstract
The tripod-like ligand N(CH2CH2PPh2)3(tdpea) forms the palladium(0) trigonal complex [Pd(tdpea)]·0.5Me2CO, (1), in which the apical nitrogen atom of the phosphine is unco-ordinated. This unsaturated species undergoes both addition (CO, SO2) and oxidative-addition reactions (alkyl halides) to form respectively tetrahedral and trigonal bipyramidal complexes. The latter contain quadridentate tdpea. Complex (1) reacts with CO2 or CS2 in the presence of O2 to form a square planar carbonate or dithiocarbonate derivative, with oxidation of a terminal PPh2 group to OPPh2. Crystal data for (1) are: a= 10.827(8)Å, α= 108.82(9)°, space group R3, and Z= 1. In the molecule the metal atom displays an unprecedented out-of-plane trigonal co-ordination. Crystal data for [Pd(tdpea)Me]I are: a= 10.570(7)Å, α= 106.10(7)°, space group R3, and Z= 1. The geometry of the [Pd(tdpea) Me]+ cation is trigonal bipyramidal, with the three-fold crystallographic axis passing through the nitrogen, the palladium, and the carbon atom.
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