PO23- and AsO3-: Pnictogenide Ligands in the Highly Charged Re4 Cluster Anions [{Re4(PO)3(PO2)}(CN)12]8-, [{Re4As2(AsO)2}(CN)12]8-, and [{Re4(AsO)4}(CN)12]8

Aleksei S Pronin; Anton I Smolentsev; Svetlana G Kozlova; Igor N Novozhilov; Yuri V Mironov

doi:10.1021/acs.inorgchem.9b00520

PO₂^3- and AsO^3-: Pnictogenide Ligands in the Highly Charged Re₄ Cluster Anions [{Re₄(PO)₃(PO₂)}(CN)₁₂]^8-, [{Re₄As₂(AsO)₂}(CN)₁₂]^8-, and [{Re₄(AsO)₄}(CN)₁₂]⁸

Inorg Chem. 2019 Jun 3;58(11):7368-7373. doi: 10.1021/acs.inorgchem.9b00520. Epub 2019 May 16.

Authors

Aleksei S Pronin¹, Anton I Smolentsev^{1

2}, Svetlana G Kozlova^{1

2}, Igor N Novozhilov¹, Yuri V Mironov^{1

2}

Affiliations

¹ Nikolaev Institute of Inorganic Chemistry Siberian Branch of the Russian Academy of Sciences , 630090 , 3, Academician Lavrentiev Avenue , Novosibirsk , Russian Federation.
² Novosibirsk State University , 630090 , 2, Pirogova Street , Novosibirsk , Russian Federation.

PMID: 31094204
DOI: 10.1021/acs.inorgchem.9b00520

Abstract

New tetrahedral anionic rhenium cluster complexes [{Re₄(PO)₃(PO₂)}(CN)₁₂]^8- (1) and [{Re₄As₂(AsO)₂}(CN)₁₂]^8- (2) have been synthesized by the reaction of ReI₃ with NaCN and P_red or KCN and As_gray, respectively. Compound 2 was further oxidized by aqueous H₂O₂ to produce the cluster anion [{Re₄(AsO)₄}(CN)₁₂]^8- (3). The anions contain new pnictogen/oxygen-based ligands, PO₂^3- and AsO^3-, which were stabilized by the coordination to the triangular faces of the tetrahedral Re₄ metallocluster in μ₃-mode. All three compounds were crystallized as either sodium or potassium salts, and their crystal structures were determined by single crystal X-ray diffraction analysis.