caa a22 4500 606181016 CHVBK 20210128100809.0 cr unu---uuuuu 210128e20150101xx s 000 0 eng 10.1007/s10876-014-0733-1 doi (NATIONALLICENCE)springer-10.1007/s10876-014-0733-1 Influence of the Diphosphine Coordinated to Molybdenum and Tungsten Triangular M3S4 Cluster Hydrides in the Catalytic Hydrodefluorination of Pentafluoropyridine [Elektronische Daten] [Carmina Alfonso, Tomás Beltrán, Marta Feliz, Rosa Llusar] Hydrido molybdenum and tungsten(IV) cluster cations of formula [M3S4H3(dppe)3]+ (dppe=1,2-(bis)dimethylphosphinoethane), [Mo-1]+ (M=Mo) and [W-1]+ (M=W), have been isolated by reacting their halide precursors with borohydride. Synthetic procedures have been optimized by appropriate choice of the solvent. Furthermore, [M3S4F3(dppe)3]+ fluorido cluster complexes, [Mo-2]+ (M=Mo) and [W-2]+ (M=W) have been prepared through halogen substitution reactions using an excess of cesium fluoride. The structures of [Mo-1]+ and [Mo-2]+ have been determined by single crystal X-ray diffraction experiments. These [M-1]+ hydrido and [M-2]+ fluorido clusters have been used as catalysts and precatalysts, respectively, in the catalytic hydrodefluorination (HDF) of pentafluoropyridine using HSiMe2Ph as hydrogen source. The reaction proceeds under microwave and reflux conditions to selectively afford 2,3,5,6-tetrafluoropyridine. The [W-1]+ hydrido cluster is the most efficient catalyst with turnover numbers of 124, while the [Mo-1]+ hydrido cluster reacts faster. Fluorido [Mo-2]+ and [W-2]+ complexes provide lower yields and turnover numbers. In general, the molybdenum and tungsten [M-1]+ and [M-2]+ diphosphino complexes are more efficient than their dmpe (1,2-(bis)dimethylphosphinoethano) analogues and activate pentafluoropyridine under softer conditions. Graphical Abstract: Springer Science+Business Media New York, 2014 Catalytic hydrodefluorination nationallicence Cluster sulphides nationallicence Group six metals nationallicence Hydrides nationallicence Fluorides nationallicence Alfonso Carmina Departament de Química Física i Analítica, Universitat Jaume I, Av. Sos Baynat s/n, 12071, Castellón de la Plana, Spain aut Beltrán Tomás Departament de Química Física i Analítica, Universitat Jaume I, Av. Sos Baynat s/n, 12071, Castellón de la Plana, Spain aut Feliz Marta Instituto de Tecnología Química, CSIC-UPV, Avda. de los Naranjos s/n, 46022, Valencia, Spain aut Llusar Rosa Departament de Química Física i Analítica, Universitat Jaume I, Av. Sos Baynat s/n, 12071, Castellón de la Plana, Spain aut Journal of Cluster Science Springer US; http://www.springer-ny.com 26/1(2015-01-01), 199-209 1040-7278 26:1<199 2015 26 10876 https://doi.org/10.1007/s10876-014-0733-1 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/s10876-014-0733-1 text/html Onlinezugriff via DOI NATIONALLICENCE 700 1- Alfonso Carmina Departament de Química Física i Analítica, Universitat Jaume I, Av. Sos Baynat s/n, 12071, Castellón de la Plana, Spain aut NATIONALLICENCE 700 1- Beltrán Tomás Departament de Química Física i Analítica, Universitat Jaume I, Av. Sos Baynat s/n, 12071, Castellón de la Plana, Spain aut NATIONALLICENCE 700 1- Feliz Marta Instituto de Tecnología Química, CSIC-UPV, Avda. de los Naranjos s/n, 46022, Valencia, Spain aut NATIONALLICENCE 700 1- Llusar Rosa Departament de Química Física i Analítica, Universitat Jaume I, Av. Sos Baynat s/n, 12071, Castellón de la Plana, Spain aut NATIONALLICENCE 773 0- Journal of Cluster Science Springer US; http://www.springer-ny.com 26/1(2015-01-01), 199-209 1040-7278 26:1<199 2015 26 10876