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Theoretical (DFT and TD\u2010DFT) calculations on the closely related cluster with L=buta\u20101,3\u2010diene (<jats:bold>2\u2032<\/jats:bold>) have revealed that the low\u2010lying electronic transitions of these [Os<jats:sub>3<\/jats:sub>(CO)<jats:sub>10<\/jats:sub>(<jats:italic>s<\/jats:italic>\u2010<jats:italic>cis<\/jats:italic>\u20101,3\u2010diene)] clusters have a predominant \u03c3(core)\u03c0*(CO) character. From the lowest \u03c3\u03c0* excited state, cluster <jats:bold>1<\/jats:bold> undergoes fast Os\uf8ffOs(1,3\u2010diene) bond cleavage (<jats:italic>\u03c4<\/jats:italic>=3.3 ps) resulting in the formation of a coordinatively unsaturated primary photoproduct (<jats:bold>1\u2009a<\/jats:bold>) with a single CO bridge. A new insight into the structure of the transient has been obtained by DFT calculations. The cleaved Os\uf8ffOs(1,3\u2010diene) bond is bridged by the donor 1,3\u2010diene ligand, compensating for the electron deficiency at the neighbouring Os centre. Because of the unequal distribution of the electron density in transient <jats:bold>1\u2009a<\/jats:bold>, a second CO bridge is formed in 20 ps in the photoproduct [Os<jats:sub>3<\/jats:sub>(CO)<jats:sub>8<\/jats:sub>(\u03bc\u2010CO)<jats:sub>2<\/jats:sub>(cyclohexa\u20101,3\u2010diene)] (<jats:bold>1\u2009b<\/jats:bold>). The latter compound, absorbing strongly around 630 nm, mainly regenerates the parent cluster with a lifetime of about 100 ns in hexane. Its structure, as suggested by the DFT calculations, again contains the 1,3\u2010diene ligand coordinated in a bridging fashion. Photoproduct <jats:bold>1\u2009b<\/jats:bold> can therefore be assigned as a high\u2010energy coordination isomer of the parent cluster with all Os\uf8ffOs bonds bridged.<\/jats:p>","DOI":"10.1002\/chem.200400086","type":"journal-article","created":{"date-parts":[[2004,5,25]],"date-time":"2004-05-25T10:05:18Z","timestamp":1085479518000},"page":"3451-3460","source":"Crossref","is-referenced-by-count":8,"title":["Low\u2010Lying Excited States and Primary Photoproducts of [Os<sub>3<\/sub>(CO)<sub>10<\/sub>(<i>s\u2010cis\u2010<\/i>L)] (L=Cyclohexa\u20101,3\u2010diene, Buta\u20101,3\u2010diene)] Clusters Studied by Picosecond Time\u2010Resolved UV\/Vis and IR Spectroscopy and by Density Functional Theory"],"prefix":"10.1002","volume":"10","author":[{"given":"Frank W.","family":"Vergeer","sequence":"first","affiliation":[]},{"given":"Pavel","family":"Matousek","sequence":"additional","affiliation":[]},{"given":"Michael","family":"Towrie","sequence":"additional","affiliation":[]},{"given":"Paulo J.","family":"Costa","sequence":"additional","affiliation":[]},{"given":"Maria J.","family":"Calhorda","sequence":"additional","affiliation":[]},{"given":"Franti\u0161ek","family":"Hartl","sequence":"additional","affiliation":[]}],"member":"311","published-online":{"date-parts":[[2004,7,8]]},"reference":[{"key":"e_1_2_6_1_2","unstructured":"\u00a0"},{"key":"e_1_2_6_2_2","doi-asserted-by":"publisher","DOI":"10.1016\/B978-008046519-7.00091-5"},{"key":"e_1_2_6_3_2","first-page":"443","volume-title":"Catalysis by Di\u2010 and Polynuclear Metal Cluster Complexes","author":"Braunstein P.","year":"1998"},{"key":"e_1_2_6_4_2","unstructured":"\u00a0"},{"key":"e_1_2_6_5_2","doi-asserted-by":"publisher","DOI":"10.1016\/S0022-328X(98)00704-9"},{"key":"e_1_2_6_6_2","doi-asserted-by":"publisher","DOI":"10.1039\/dt9950002923"},{"key":"e_1_2_6_7_2","doi-asserted-by":"publisher","DOI":"10.1021\/ic9707319"},{"key":"e_1_2_6_8_2","doi-asserted-by":"publisher","DOI":"10.1016\/S0022-328X(98)01197-8"},{"key":"e_1_2_6_9_2","doi-asserted-by":"publisher","DOI":"10.1016\/0022-328X(96)06186-4"},{"key":"e_1_2_6_10_2","unstructured":"\u00a0"},{"key":"e_1_2_6_11_2","doi-asserted-by":"publisher","DOI":"10.1016\/0009-2614(95)00124-M"},{"key":"e_1_2_6_12_2","doi-asserted-by":"publisher","DOI":"10.1016\/0009-2614(94)00812-4"},{"key":"e_1_2_6_13_2","unstructured":"\u00a0"},{"key":"e_1_2_6_14_2","doi-asserted-by":"publisher","DOI":"10.1002\/1521-3757(20010803)113:15<2889::AID-ANGE2889>3.0.CO;2-I"},{"key":"e_1_2_6_14_3","doi-asserted-by":"publisher","DOI":"10.1002\/1521-3773(20010803)40:15<2809::AID-ANIE2809>3.0.CO;2-U"},{"key":"e_1_2_6_15_2","doi-asserted-by":"publisher","DOI":"10.1021\/ja010648r"},{"key":"e_1_2_6_16_2","doi-asserted-by":"publisher","DOI":"10.1063\/1.466334"},{"key":"e_1_2_6_17_2","doi-asserted-by":"publisher","DOI":"10.1021\/j100089a007"},{"key":"e_1_2_6_18_2","unstructured":"\u00a0"},{"key":"e_1_2_6_19_2","doi-asserted-by":"publisher","DOI":"10.1021\/ja003344y"},{"key":"e_1_2_6_20_2","doi-asserted-by":"publisher","DOI":"10.1063\/1.472858"},{"key":"e_1_2_6_21_2","doi-asserted-by":"publisher","DOI":"10.1039\/b201272c"},{"key":"e_1_2_6_22_2","doi-asserted-by":"publisher","DOI":"10.1039\/B303437B"},{"key":"e_1_2_6_23_2","doi-asserted-by":"publisher","DOI":"10.1016\/S0020-1693(99)00560-5"},{"key":"e_1_2_6_24_2","doi-asserted-by":"publisher","DOI":"10.1002\/1521-3765(20020402)8:7<1741::AID-CHEM1741>3.0.CO;2-Z"},{"key":"e_1_2_6_25_2","doi-asserted-by":"publisher","DOI":"10.1039\/b108792d"},{"key":"e_1_2_6_26_2","unstructured":"\u00a0"},{"key":"e_1_2_6_27_2","doi-asserted-by":"publisher","DOI":"10.1021\/om00072a032"},{"key":"e_1_2_6_28_2","doi-asserted-by":"publisher","DOI":"10.1021\/ic00142a047"},{"key":"e_1_2_6_29_2","doi-asserted-by":"publisher","DOI":"10.1021\/ja00093a024"},{"key":"e_1_2_6_30_2","doi-asserted-by":"publisher","DOI":"10.1021\/ja00431a055"},{"key":"e_1_2_6_31_2","doi-asserted-by":"publisher","DOI":"10.1021\/ic50185a057"},{"key":"e_1_2_6_32_2","doi-asserted-by":"publisher","DOI":"10.1016\/0020-1693(95)90077-J"},{"key":"e_1_2_6_33_2","unstructured":"\u00a0"},{"key":"e_1_2_6_34_2","doi-asserted-by":"publisher","DOI":"10.1002\/1099-0682(20011)2001:1<223::AID-EJIC223>3.0.CO;2-U"},{"key":"e_1_2_6_35_2","doi-asserted-by":"publisher","DOI":"10.1021\/ic9905289"},{"key":"e_1_2_6_36_2","doi-asserted-by":"publisher","DOI":"10.1016\/0022-328X(90)85141-K"},{"key":"e_1_2_6_37_2","doi-asserted-by":"publisher","DOI":"10.1016\/S0010-8545(98)90017-0"},{"key":"e_1_2_6_38_2","first-page":"933","volume":"200","author":"Stufkens D. 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