Nature of M–Bi bonds in dihalobismuth complexes of nickel, palladium and platinum trans-[X(PMe3)2M(BiX2] (M = Ni, Pd, Pt; X = Cl, Br, I): A theoretical study
✍ Scribed by Krishna K. Pandey
- Publisher
- Elsevier
- Year
- 2011
- Tongue
- English
- Weight
- 596 KB
- Volume
- 967
- Category
- Article
- ISSN
- 2210-271X
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✦ Synopsis
Geometry, electronic structure and bonding energy analysis of the terminal neutral dihalobismuth complexes of nickel, palladium and platinum trans-[X(PMe 3 ) 2 M(BiX 2 )] (M = Ni, Pd, Pt; X = Cl, Br, I) were investigated at the BP86/TZ2P/ZORA level of theory. The calculated geometrical parameters of platinum complex trans-[Cl(PMe 3 ) 2 Pt(BiCl 2 )] are in excellent agreement with structurally characterized platinum complex trans-[Cl(PCy 3 ) 2 Pt(BiCl 2 )]. The variations in the M-Bi bond distances show that the trans effect of halides is relatively greater than the effects of halides bonded to the Bi atom. Hence, the strength of the M-Bi bond decreases on going from X = Cl to X = I in the complexes trans-[X(PMe 3 ) 2 M(BiX 2 )]. From the perspective of covalent bonding, however p-symmetry contributions are, in all complexes, significantly smaller than the corresponding r bonding contribution. Thus, in these complexes, the [BiX 2 ] behaves predominantly as a r donor. The natural population analysis (NPA) charge distributions indicate the bismuth atom carries a significant positive charge in all cases. The contributions of the electrostatic interactions DE elstat are significantly larger in all bismuth complexes (I-IX) than the covalent bonding DE orb. The interaction energy increases in the order Ni < Pd < Pt, and the absolute values of the DE Pauli , DE int and DE elstat contributions to the M-Bi bonds decrease according to X = Cl > Br > I.