On the Nature of Bonding in Synthetic Charged Molecular Alloy [P₇ZnP₇]^4- Cluster and Its Relevant [P₇]^3- Zintl Ion.

ABSTRACT: Charged molecular alloys and Zintl ions are of interest in synthetic chemistry. However, their chemical bonding has seldom been elucidated using modern quantum chemistry tools. Herein, we report on in-depth chemical bonding analyses for a charged molecular alloy C ₂ [P₇ZnP₇]^4- cluster and its relevant Zintl ion C _3v [P₇]^3- ligand, making use of electronic structure calculations at PBE0/def2-TZVP level, natural bond orbital and orbital composition analyses, canonical molecular orbitals, and adaptive natural density partitioning (AdNDP). The computational data show that C _3v [P₇]^3- Zintl ion has three isolated, negatively charged, bridging P sites. Such charges are largely P 3p lone-pairs in nature, but they also participate in secondary P-P bonding along the bridging sites. C ₂ [P₇ZnP₇]^4- cluster is formulated as [P₇]^2-[Zn]⁰[P₇]^2-, in which [P₇]^2- ligands maintain the structural and bonding integrity of [P₇]^3- Zintl ion despite their difference in charge state. Two [P₇]^2- ligands collectively bind with Zn center via four bridging P sites, resulting in a quasi-tetrahedral ZnP₄ core with the eight-electron counting. This bonding picture can alternatively be rationalized using the superatom concept. The Zn-P bonds are weak with a bond order of around 0.5, because the P centers have partial nonbonding 3p character, akin to 3p² lone-pairs albeit with a lower occupation number.

SUBMITTER: You XR 

PROVIDER: S-EPMC6645155 | biostudies-literature | 2018 Sep

REPOSITORIES: biostudies-literature