Polynuclear Rhenium and Manganese Selenido-Carbonyl Complexes − Reversible Square to Butterfly Conversion of the Re4Se2 Core by CO Loss in [Re4(µ3-Se)2(CO)16(PPh3)2], and the Crystal Structure of [Mn2(µ2-Se2)(CO)5(PPh3)2]

• Published in: European journal of inorganic chemistry Vol. 2004; no. 17; pp. 3564 - 3569
• Main Authors: Belletti, Daniele, Graiff, Claudia, Pattacini, Roberto, Predieri, Giovanni, Tiripicchio, Antonio
• Format: Journal Article
• Language: English
• Published: Weinheim WILEY-VCH Verlag 06.09.2004; WILEY‐VCH Verlag
• Subjects: Cluster compounds; Manganese; Rhenium; Selenium
• ISSN: 1434-1948; 1099-0682
• DOI: 10.1002/ejic.200400090

The reaction of Ph3PSe with [Mn2(CO)10] leads to the formation of [Mn4(μ3‐Se)2(μ‐CO)(CO)14(PPh3)2], which contains a butterfly “Mn2Se2 core”, along with traces of [Mn2(μ2‐Se2)(CO)5(PPh3)2] (1), which contains a tetrahedral Mn2Se2 core. The reaction of Ph3PSe with [Re2(CO)8(NCMe)2] affords two new complexes, [Re4(μ3‐Se)2(CO)16(PPh3)2] (2) and [Re4(μ3‐Se)2(μ‐CO)(CO)14(PPh3)2] (3). Their molecular structures, determined by X‐ray diffraction methods, exhibit a nearly square‐planar Re2Se2 and a butterfly Re2Se2 core, respectively. These air‐stable tetrarhenium selenido‐carbonyl species display a reversible loss/addition of a CO molecule, which is accompanied by the formation/cleavage of a Re−Re bond and the consequent rearrangement of the Re2Se2 core, from square to butterfly and vice versa. (© Wiley‐VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany, 2004)