Relativistic density functional theory (DFT) calculations of the geometries and Au-P bonding of W@Au12PX3 (X = H, F, Cl, Br, I, Me, OMe) and M@Au-12(PH3)-P-q (M-q = Hf2-, Ta-, W, Re+, Os2+, Ir3+, pt(4+), Au5+) have been carried out. There are some regular changes in geometry and binding of these two kinds of complexes with the variation of the phosphanes PX3 and transition metals M-q. The energy decomposition analysis confirms that the PX3 ligands are sigma donors. The donor tendency (Delta E-sigma/Delta E-pi) decreases for different X with increasing electronegativity and for different Mq from Au5+ to Hf2-, while the pi-back-donation increases in the same direction. The calculated P-H bond lengths show a regular decrease from Hf2- to Ir3+, but have abnormal trends for pt(4+) and Au5+.
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