caa a22 4500 463184718 CHVBK 20180406164849.0 cr unu---uuuuu 170326e20070401xx s 000 0 eng 10.1007/s10870-006-9132-2 doi (NATIONALLICENCE)springer-10.1007/s10870-006-9132-2 Photochemical reactivity of the triosmium cluster 1,1-Os3(CO)10(bpcd) in the presence of P(OEt)3 and X-ray crystal structure of HOs3(CO)7[P(OEt)3][μ-{PPh(C6H4)} C=C(PPh2)C(O)CH2C(O)]: Unexpected ortho metalation and cluster face capping by a diphosphine ligand [Elektronische Daten] [William Watson, Alex Strugatskiy, Guanmin Wu, Michael Richmond] Photochemical activation of the bpcd-chelated cluster 1,1-Os3(CO)10(bpcd) (1) in the presence of P(OEt)3 furnishes the simple substitution product 1,1,2-Os3(CO)9[P(OEt)3](bpcd) (2) initially, followed by the formation of the hydride cluster HOs3(CO)7[P(OEt)3][μ-{PPh(C6H4)}C=C(PPh2)C(O)CH2C(O)] (3). Both new clusters were isolated and characterized in solution by IR and NMR (1H and 31P) spectroscopies, with the solid-state structure of cluster 3 determined by X-ray diffraction analysis. Cluster 3 crystallizes in the triclinic space group P−1, a=9.366(2)Å, b=14.182(4)Å, c=17.672(4)Å, α=87.787(4)°, β=78.488(4)°, γ=71.785(4)°, V=2184.1(9)Å3, Z=2, D cacl=2.123Mg/m3; R=0.0488, R w=0.1059 for 8527 observed reflections with I > 2σ(I). The presence of the seven-electron ligand μ-P{Ph(C6H4)}C=C(PPh2)C(O)CH2C(O) that caps one of the triangular faces in 3 through both phosphine moieties, the π bond of the dione ring, and an ortho-metalated aryl ligand is established. Springer Science+Business Media, Inc., 2007 triosmium clusters nationallicence diphosphine ligand nationallicence ligand substitution nationallicence ortho metalation nationallicence Watson William Department of Chemistry, Texas Christian University, 76129, Fort Worth, TX, USA aut Strugatskiy Alex Department of Chemistry, University of North Texas, 76203, Denton, TX, USA aut Wu Guanmin Department of Chemistry, University of North Texas, 76203, Denton, TX, USA aut Richmond Michael Department of Chemistry, University of North Texas, 76203, Denton, TX, USA aut Journal of Chemical Crystallography Kluwer Academic Publishers-Plenum Publishers; http://www.springer-ny.com 37/4(2007-04-01), 247-253 1074-1542 37:4<247 2007 37 10870 https://doi.org/10.1007/s10870-006-9132-2 text/html Onlinezugriff via DOI 1 research-article jats NATIONALLICENCE 856 40 https://doi.org/10.1007/s10870-006-9132-2 text/html Onlinezugriff via DOI NATIONALLICENCE 700 1- Watson William Department of Chemistry, Texas Christian University, 76129, Fort Worth, TX, USA aut NATIONALLICENCE 700 1- Strugatskiy Alex Department of Chemistry, University of North Texas, 76203, Denton, TX, USA aut NATIONALLICENCE 700 1- Wu Guanmin Department of Chemistry, University of North Texas, 76203, Denton, TX, USA aut NATIONALLICENCE 700 1- Richmond Michael Department of Chemistry, University of North Texas, 76203, Denton, TX, USA aut NATIONALLICENCE 773 0- Journal of Chemical Crystallography Kluwer Academic Publishers-Plenum Publishers; http://www.springer-ny.com 37/4(2007-04-01), 247-253 1074-1542 37:4<247 2007 37 10870 Metadata rights reserved Springer special CC-BY-NC licence nationallicence BK010053 XK010053 XK010000 NATIONALLICENCE NATIONALLICENCE NL-springer