caa a22 4500 606180834 CHVBK 20210128100808.0 cr unu---uuuuu 210128e20150101xx s 000 0 eng 10.1007/s10876-014-0720-6 doi (NATIONALLICENCE)springer-10.1007/s10876-014-0720-6 Linkage Isomerism in [Mo3(μ3-S)(μ2-SSe)3(dtp)3]Cl: Preparation and Characterization of Two Isomers with Different Coordination Mode of the μ2-SSe Ligand [Elektronische Daten] [Rita Hernández-Molina, Artem Gushchin, Cristian Vicent, Pedro Gili] Two geometrical isomers of the composition [Mo3S4Se3(dtp)3]Cl (dtp is O,O′-diethyldithiophosphate) have been prepared and characterized by multinuclear NMR, electrospray ionization mass spectrometry (ESI-MS) and quantum chemical calculations. The first isomer was prepared by reaction of the aqua cluster ([Mo3(μ3-S)(μ2-Se)3(H2O)9]4+) with a large excess of P4S10/EtOH in 2M HCl. Its structure corresponds to [Mo3(μ3-S)(μ2-Seax-Seq)3(dtp)3]Cl (1). The second isomer, [Mo3(μ3-S)(μ2-Sax-Seeq)3(dtp)3]Cl (2) was prepared by the reaction of [Mo3S7Cl6]2− with SePPh3 followed by treatment with a stoichiometric amount of P4S10/EtOH. The reason for the isomerism is that the μ2-SSe ligand is coordinated asymmetrically, so that one chalcogen atom is almost coplanar with the Mo3 plane (called equatorial) and the other one is strongly out of the plane (axial). Alternative occupancy of these positions by S or Se leads to a rare kind of linkage isomerism. Each isomer has distinctive spectroscopic signature and fragmentation pattern in ESI-MS. Isomer 2 with μ2-SaxSeeq coordination mode was found to be slightly more stable than isomer 1 with μ2-SeaxSeq coordination. Graphical Abstract: Two new geometrical isomers (1) and (2) of the composition [Mo3(µ3-S)(µ2-Seax-Seq)3(dtp)3]Cl and [Mo3(µ3-S)(µ2-Seq-Seax)3(dtp)3]Cl have been prepared and characterized by multinuclear NMR, electrospray ionization, mass spectrometry (ESI-MS) and quantum chemical calculations. Springer Science+Business Media New York, 2014 Molybdenum clusters nationallicence Chalcogenide clusters nationallicence Linkage isomerism nationallicence Dithiophosphates nationallicence Crystal structure nationallicence Hernández-Molina Rita Departamento de Química Inorgánica, 38200, La Laguna, Tenerife aut Gushchin Artem Nikolaev Institute of Inorganic Chemistry of the Russian Academy of Sciences, Novosibirsk, Russia aut Vicent Cristian Serveis Centrals d'Instrumentació Científica, Universitat Jaume I, Avda. Sos Baynat, Castellón de la Plana, Spain aut Gili Pedro Departamento de Química Inorgánica, 38200, La Laguna, Tenerife aut Journal of Cluster Science Springer US; http://www.springer-ny.com 26/1(2015-01-01), 83-91 1040-7278 26:1<83 2015 26 10876 https://doi.org/10.1007/s10876-014-0720-6 text/html Onlinezugriff via DOI BK010053 XK010053 XK010000 Metadata rights reserved Springer special CC-BY-NC licence nationallicence 1 research-article jats NATIONALLICENCE NATIONALLICENCE NL-springer NATIONALLICENCE 856 40 https://doi.org/10.1007/s10876-014-0720-6 text/html Onlinezugriff via DOI NATIONALLICENCE 700 1- Hernández-Molina Rita Departamento de Química Inorgánica, 38200, La Laguna, Tenerife aut NATIONALLICENCE 700 1- Gushchin Artem Nikolaev Institute of Inorganic Chemistry of the Russian Academy of Sciences, Novosibirsk, Russia aut NATIONALLICENCE 700 1- Vicent Cristian Serveis Centrals d'Instrumentació Científica, Universitat Jaume I, Avda. Sos Baynat, Castellón de la Plana, Spain aut NATIONALLICENCE 700 1- Gili Pedro Departamento de Química Inorgánica, 38200, La Laguna, Tenerife aut NATIONALLICENCE 773 0- Journal of Cluster Science Springer US; http://www.springer-ny.com 26/1(2015-01-01), 83-91 1040-7278 26:1<83 2015 26 10876