caa a22 4500 606180869 CHVBK 20210128100808.0 cr unu---uuuuu 210128e20150101xx s 000 0 eng 10.1007/s10876-014-0756-7 doi (NATIONALLICENCE)springer-10.1007/s10876-014-0756-7 Synthesis of the Stereoisomeric Clusters 1,2-Os3(CO)10( trans -dpmn) and 1,2-Os3(CO)10( cis -dpmn) [where dpmn=2,3-bis(diphenylphosphinomethyl)-5-norbornene]: DFT Evaluation of the Isomeric Clusters 1,2-Os3(CO)10(dpmn) and Isomer-Dependent Diphosphine Ligand Activation [Elektronische Daten] [Li Yang, Vladimir Nesterov, Xiaoping Wang, Michael Richmond] The bicyclic diphosphines trans- and cis-2,3-bis(diphenylphosphinomethyl)-5-norbornene (dpmn) react with 1,2-Os3(CO)10(MeCN)2 (1) to furnish the corresponding ligand-bridged clusters Os3(CO)10(trans-dpmn) (2) and Os3(CO)10(cis-dpmn) (3). Both new products have been isolated and the molecular structures established by X-ray diffraction analyses. The dihydroxyl-bridged cluster 1,2-Os3(CO)8(µ-OH)2(cis-dpmn) (4), which accompanied the formation of 3 in one reaction, has been isolated and characterized by mass spectrometry and X-ray crystallography. Whereas cluster 2 is stable in toluene at 373K, 3 is thermally sensitive under identical conditions and undergoes loss of CO (2 equiv), coupled with the activation of three norbornene C-H bonds and one P-C(phenyl) bond, to furnish the dihydride cluster H2Os3(CO)8[µ3-2-PhPC-3-endo-Ph2PCH2(C7H7)] (5). The solid-state structure of 5 confirms the multiple activation of the cis-dpmn ligand and accompanying formation of the face-capping 2-PhPC-3-endo-Ph2PCH2(C7H7) moiety in the product. DFT calculations on 2 and 3 indicate that the former cluster is the thermodynamically more stable isomer, and the conversion of 3→5+2CO+benzene is computed to be exergonic by 12.7kcal/mol and is entropically favored due to the release of the CO and benzene by-products. Springer Science+Business Media New York, 2014 Osmium clusters nationallicence Ligand substitution nationallicence Diphosphine ligand activation nationallicence X-ray crystallography nationallicence DFT nationallicence Yang Li Department of Chemistry, University of North Texas, 76203, Denton, TX, USA aut Nesterov Vladimir Department of Chemistry, University of North Texas, 76203, Denton, TX, USA aut Wang Xiaoping Neutron Sciences Directorate, Oak Ridge National Laboratory, 37831, Oak Ridge, TN, USA aut Richmond Michael Department of Chemistry, University of North Texas, 76203, Denton, TX, USA aut Journal of Cluster Science Springer US; http://www.springer-ny.com 26/1(2015-01-01), 93-109 1040-7278 26:1<93 2015 26 10876 https://doi.org/10.1007/s10876-014-0756-7 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/s10876-014-0756-7 text/html Onlinezugriff via DOI NATIONALLICENCE 700 1- Yang Li Department of Chemistry, University of North Texas, 76203, Denton, TX, USA aut NATIONALLICENCE 700 1- Nesterov Vladimir Department of Chemistry, University of North Texas, 76203, Denton, TX, USA aut NATIONALLICENCE 700 1- Wang Xiaoping Neutron Sciences Directorate, Oak Ridge National Laboratory, 37831, Oak Ridge, TN, USA aut NATIONALLICENCE 700 1- Richmond Michael Department of Chemistry, University of North Texas, 76203, Denton, TX, USA aut NATIONALLICENCE 773 0- Journal of Cluster Science Springer US; http://www.springer-ny.com 26/1(2015-01-01), 93-109 1040-7278 26:1<93 2015 26 10876