{"status":"ok","message-type":"work","message-version":"1.0.0","message":{"indexed":{"date-parts":[[2025,10,15]],"date-time":"2025-10-15T00:41:27Z","timestamp":1760488887767,"version":"build-2065373602"},"reference-count":79,"publisher":"Wiley","issue":"18","license":[{"start":{"date-parts":[[2007,5,10]],"date-time":"2007-05-10T00:00:00Z","timestamp":1178755200000},"content-version":"vor","delay-in-days":0,"URL":"http:\/\/onlinelibrary.wiley.com\/termsAndConditions#vor"}],"content-domain":{"domain":["chemistry-europe.onlinelibrary.wiley.com"],"crossmark-restriction":true},"short-container-title":["Eur J Inorg Chem"],"published-print":{"date-parts":[[2007,6]]},"abstract":"<jats:title>Abstract<\/jats:title><jats:p>The reactions of [Mo(CO)<jats:sub>2<\/jats:sub>(Cp)(NCCH<jats:sub>3<\/jats:sub>)<jats:sub>2<\/jats:sub>][BF<jats:sub>4<\/jats:sub>] (<jats:bold>1<\/jats:bold>) with spiro[2.4]hepta\u20104,6\u2010diene and spiro[4.4]nona\u20101,3\u2010diene give the complexes [Mo{\u03b7<jats:sup>4<\/jats:sup>\u2010C<jats:sub>5<\/jats:sub>H<jats:sub>4<\/jats:sub>(CH<jats:sub>2<\/jats:sub>)<jats:sub>2<\/jats:sub>}(CO)<jats:sub>2<\/jats:sub>(Cp)][BF<jats:sub>4<\/jats:sub>] (<jats:bold>3<\/jats:bold>) and [Mo{\u03b7<jats:sup>4<\/jats:sup>\u2010C<jats:sub>5<\/jats:sub>H<jats:sub>4<\/jats:sub>(CH<jats:sub>2<\/jats:sub>)<jats:sub>4<\/jats:sub>}(CO)<jats:sub>2<\/jats:sub>(Cp)][BF<jats:sub>4<\/jats:sub>] (<jats:bold>4<\/jats:bold>), respectively. [Mo{\u03b7<jats:sup>4<\/jats:sup>\u2010C<jats:sub>5<\/jats:sub>H<jats:sub>4<\/jats:sub>(CH<jats:sub>2<\/jats:sub>)<jats:sub>2<\/jats:sub>}(CO)<jats:sub>2<\/jats:sub>(Cp)][BF<jats:sub>4<\/jats:sub>] (<jats:bold>3<\/jats:bold>) is stable towards ring opening at room temperature, but its formation is accompanied by small amounts of ring\u2010opening products [Mo(\u03b7<jats:sup>5<\/jats:sup>\u2010C<jats:sub>5<\/jats:sub>H<jats:sub>4<\/jats:sub>CH<jats:sub>2<\/jats:sub>\u2010\u03b7<jats:sup>1<\/jats:sup>\u2010CH<jats:sub>2<\/jats:sub>)(CO)(Cp)][BF<jats:sub>4<\/jats:sub>] (<jats:bold>5<\/jats:bold>) and [Mo{\u03b7<jats:sup>5<\/jats:sup>\u2010C<jats:sub>5<\/jats:sub>H<jats:sub>4<\/jats:sub>(CH<jats:sub>2<\/jats:sub>)<jats:sub>2<\/jats:sub>\u2010\u03b7<jats:sup>1<\/jats:sup>\u2010CO}(CO)(Cp)][BF<jats:sub>4<\/jats:sub>] (<jats:bold>6<\/jats:bold>). With 1,1\u2010dimethyl\u2010spiro[2.4]hepta\u20104,6\u2010diene, two isomers with the formula [Mo{\u03b7<jats:sup>4<\/jats:sup>\u2010C<jats:sub>5<\/jats:sub>H<jats:sub>4<\/jats:sub>CH<jats:sub>2<\/jats:sub>C(CH<jats:sub>3<\/jats:sub>)<jats:sub>2<\/jats:sub>}(CO)<jats:sub>2<\/jats:sub>(Cp)][BF<jats:sub>4<\/jats:sub>] are formed (<jats:bold>7<\/jats:bold> and <jats:bold>8<\/jats:bold>). While the <jats:italic>endo<\/jats:italic>\u2010isomer <jats:bold>7<\/jats:bold> is stable towards ring opening, the <jats:italic>exo<\/jats:italic>\u2010isomer <jats:bold>8<\/jats:bold> slowly rearranges to the ring\u2010opened product [Mo{\u03b7<jats:sup>5<\/jats:sup>\u2010C<jats:sub>5<\/jats:sub>H<jats:sub>4<\/jats:sub>C(CH<jats:sub>3<\/jats:sub>)<jats:sub>2<\/jats:sub>CH<jats:sub>2<\/jats:sub>\u2010\u03b7<jats:sup>1<\/jats:sup>\u2010CO}(CO)(Cp)][BF<jats:sub>4<\/jats:sub>] (<jats:bold>9<\/jats:bold>). The reaction of [Mo(CO)<jats:sub>2<\/jats:sub>(Ind)(NCCH<jats:sub>3<\/jats:sub>)<jats:sub>2<\/jats:sub>][BF<jats:sub>4<\/jats:sub>] (<jats:bold>2<\/jats:bold>) with spiro[4.4]nona\u20101,3\u2010diene also gives the diene coordinated species [Mo{\u03b7<jats:sup>4<\/jats:sup>\u2010C<jats:sub>5<\/jats:sub>H<jats:sub>4<\/jats:sub>(CH<jats:sub>2<\/jats:sub>)<jats:sub>4<\/jats:sub>}(CO)<jats:sub>2<\/jats:sub>(Ind)][BF<jats:sub>4<\/jats:sub>] (<jats:bold>11<\/jats:bold>), which is the first example of a structurally characterized, coordinated, unsubstituted spirodiene. In contrast, reaction of <jats:bold>2<\/jats:bold> with spiro[2.4]hepta\u20104,6\u2010diene leads directly to the <jats:italic>ansa<\/jats:italic>\u2010cyclopentadienyl complex [Mo(\u03b7<jats:sup>5<\/jats:sup>\u2010C<jats:sub>5<\/jats:sub>H<jats:sub>4<\/jats:sub>CH<jats:sub>2<\/jats:sub>\u2010\u03b7<jats:sup>1<\/jats:sup>\u2010CH<jats:sub>2<\/jats:sub>)(CO)(Ind)][BF<jats:sub>4<\/jats:sub>] (<jats:bold>12<\/jats:bold>). Reaction of <jats:bold>12<\/jats:bold> with bromine or iodine leads to the formation of Cp\u2010substituted molybdenocene derivatives [Mo{\u03b7<jats:sup>5<\/jats:sup>\u2010C<jats:sub>5<\/jats:sub>H<jats:sub>4<\/jats:sub>(CH<jats:sub>2<\/jats:sub>)<jats:sub>2<\/jats:sub>X}(CO)(Ind)X][BF<jats:sub>4<\/jats:sub>] (<jats:bold>13<\/jats:bold>: X = Br, <jats:bold>14<\/jats:bold>: X = I). The compounds [Mo(\u03b7<jats:sup>5<\/jats:sup>\u2010C<jats:sub>5<\/jats:sub>H<jats:sub>4<\/jats:sub>CH<jats:sub>2<\/jats:sub>\u2010\u03b7<jats:sup>1<\/jats:sup>\u2010CH<jats:sub>2<\/jats:sub>)(CO)(Ind)][BF<jats:sub>4<\/jats:sub>] (<jats:bold>12<\/jats:bold>) and [MoBr{\u03b7<jats:sup>5<\/jats:sup>\u2010C<jats:sub>5<\/jats:sub>H<jats:sub>4<\/jats:sub>(CH<jats:sub>2<\/jats:sub>)<jats:sub>2<\/jats:sub>Br}(CO)(Ind)][Br]<jats:bold>\u00b7<\/jats:bold>0.5H<jats:sub>2<\/jats:sub>O (<jats:bold>13a<\/jats:bold>) were structurally characterized, and they open the way to new functionalized molybdenocene complexes that have biological applications.(\u00a9 Wiley\u2010VCH Verlag GmbH &amp; Co. KGaA, 69451 Weinheim, Germany, 2007)<\/jats:p>","DOI":"10.1002\/ejic.200700121","type":"journal-article","created":{"date-parts":[[2007,5,10]],"date-time":"2007-05-10T08:50:40Z","timestamp":1178787040000},"page":"2827-2838","update-policy":"https:\/\/doi.org\/10.1002\/crossmark_policy","source":"Crossref","is-referenced-by-count":21,"title":["Synthesis, Characterization and Stability of Spirodiene Complexes of Molybdenum(II): New Route to <i>ansa<\/i>\u2010Molybdenocene and Ring\u2010Functionalized Molybdenocene Compounds"],"prefix":"10.1002","volume":"2007","author":[{"given":"Jan","family":"Honz\u00ed\u010dek","sequence":"first","affiliation":[]},{"given":"Filipe A.","family":"Almeida Paz","sequence":"additional","affiliation":[]},{"given":"Carlos C.","family":"Rom\u00e3o","sequence":"additional","affiliation":[]}],"member":"311","published-online":{"date-parts":[[2007,6,18]]},"reference":[{"key":"e_1_2_7_1_2","doi-asserted-by":"publisher","DOI":"10.1002\/anie.197904771"},{"key":"e_1_2_7_2_2","doi-asserted-by":"publisher","DOI":"10.1021\/om060133e"},{"key":"e_1_2_7_3_2","doi-asserted-by":"publisher","DOI":"10.1021\/ic050687u"},{"key":"e_1_2_7_4_2","unstructured":"\u00a0"},{"key":"e_1_2_7_5_2","doi-asserted-by":"publisher","DOI":"10.1021\/ic9902469"},{"key":"e_1_2_7_6_2","doi-asserted-by":"publisher","DOI":"10.1016\/S0162-0134(00)00236-1"},{"key":"e_1_2_7_7_2","unstructured":"\u00a0"},{"key":"e_1_2_7_8_2","doi-asserted-by":"publisher","DOI":"10.1002\/1521-3773(20010817)40:16<3062::AID-ANIE3062>3.0.CO;2-O"},{"key":"e_1_2_7_9_2","doi-asserted-by":"publisher","DOI":"10.1007\/s00259-002-0900-8"},{"key":"e_1_2_7_10_2","unstructured":"\u00a0"},{"key":"e_1_2_7_11_2","doi-asserted-by":"publisher","DOI":"10.1021\/om030403i"},{"key":"e_1_2_7_12_2","doi-asserted-by":"publisher","DOI":"10.1021\/om049679w"},{"key":"e_1_2_7_13_2","doi-asserted-by":"publisher","DOI":"10.1021\/ja054185r"},{"key":"e_1_2_7_14_2","doi-asserted-by":"publisher","DOI":"10.1021\/cr020002x"},{"key":"e_1_2_7_15_2","unstructured":"\u00a0"},{"key":"e_1_2_7_16_2","doi-asserted-by":"publisher","DOI":"10.1016\/S0162-0134(00)00203-8"},{"key":"e_1_2_7_17_2","doi-asserted-by":"publisher","DOI":"10.1016\/j.jinorgbio.2004.09.001"},{"key":"e_1_2_7_18_2","doi-asserted-by":"publisher","DOI":"10.1016\/j.ejphar.2006.01.056"},{"key":"e_1_2_7_19_2","unstructured":"\u00a0"},{"key":"e_1_2_7_20_2","doi-asserted-by":"publisher","DOI":"10.1016\/j.jorganchem.2004.08.014"},{"key":"e_1_2_7_21_2","doi-asserted-by":"publisher","DOI":"10.1021\/ic048824v"},{"key":"e_1_2_7_22_2","doi-asserted-by":"publisher","DOI":"10.1021\/ic034892q"},{"key":"e_1_2_7_23_2","doi-asserted-by":"publisher","DOI":"10.1016\/j.bmc.2006.08.015"},{"key":"e_1_2_7_24_2","unstructured":"\u00a0"},{"key":"e_1_2_7_25_2","doi-asserted-by":"publisher","DOI":"10.1021\/om00008a042"},{"key":"e_1_2_7_26_2","doi-asserted-by":"publisher","DOI":"10.1016\/S0022-328X(98)01143-7"},{"key":"e_1_2_7_27_2","doi-asserted-by":"publisher","DOI":"10.1021\/om00159a015"},{"key":"e_1_2_7_28_2","doi-asserted-by":"publisher","DOI":"10.1021\/ja00201a022"},{"key":"e_1_2_7_29_2","doi-asserted-by":"publisher","DOI":"10.1021\/ja003339u"},{"key":"e_1_2_7_30_2","unstructured":"\u00a0"},{"key":"e_1_2_7_31_2","doi-asserted-by":"publisher","DOI":"10.1039\/b100372k"},{"key":"e_1_2_7_32_2","doi-asserted-by":"publisher","DOI":"10.1016\/S0022-328X(00)82709-6"},{"key":"e_1_2_7_33_2","doi-asserted-by":"publisher","DOI":"10.1039\/DT9950000395"},{"key":"e_1_2_7_34_2","unstructured":"\u00a0"},{"key":"e_1_2_7_35_2","doi-asserted-by":"publisher","DOI":"10.1039\/C39810000156"},{"key":"e_1_2_7_36_2","doi-asserted-by":"publisher","DOI":"10.1016\/S0022-328X(00)00218-7"},{"key":"e_1_2_7_37_2","doi-asserted-by":"publisher","DOI":"10.1039\/DT9830000861"},{"key":"e_1_2_7_38_2","doi-asserted-by":"publisher","DOI":"10.1016\/0022-328X(90)87233-4"},{"key":"e_1_2_7_39_2","doi-asserted-by":"publisher","DOI":"10.1002\/cber.19761090427"},{"key":"e_1_2_7_40_2","unstructured":"\u00a0"},{"key":"e_1_2_7_41_2","doi-asserted-by":"publisher","DOI":"10.1039\/DT9770002365"},{"key":"e_1_2_7_42_2","doi-asserted-by":"publisher","DOI":"10.1021\/om00014a011"},{"key":"e_1_2_7_43_2","doi-asserted-by":"publisher","DOI":"10.1016\/0022-328X(94)05061-F"},{"key":"e_1_2_7_44_2","unstructured":"\u00a0"},{"key":"e_1_2_7_45_2","doi-asserted-by":"publisher","DOI":"10.1016\/S0022-328X(00)89724-7"},{"key":"e_1_2_7_46_2","doi-asserted-by":"publisher","DOI":"10.1002\/cber.19801130616"},{"key":"e_1_2_7_47_2","doi-asserted-by":"publisher","DOI":"10.1016\/S0022-328X(00)85908-2"},{"key":"e_1_2_7_48_2","doi-asserted-by":"publisher","DOI":"10.1002\/cber.19761090919"},{"key":"e_1_2_7_49_2","doi-asserted-by":"publisher","DOI":"10.1021\/om970703y"},{"key":"e_1_2_7_50_2","unstructured":"\u00a0"},{"key":"e_1_2_7_51_2","doi-asserted-by":"publisher","DOI":"10.1002\/cber.19711040914"},{"key":"e_1_2_7_52_2","first-page":"2780","volume":"104","author":"M\u00fcller H.","year":"1971","journal-title":"Chem. Ber."},{"key":"e_1_2_7_53_2","unstructured":"\u00a0"},{"key":"e_1_2_7_54_2","doi-asserted-by":"publisher","DOI":"10.1107\/S0108768102003890"},{"key":"e_1_2_7_55_2","doi-asserted-by":"publisher","DOI":"10.1107\/S0108768102004895"},{"key":"e_1_2_7_56_2","doi-asserted-by":"publisher","DOI":"10.1021\/om00124a022"},{"key":"e_1_2_7_57_2","doi-asserted-by":"publisher","DOI":"10.1021\/om00111a012"},{"key":"e_1_2_7_58_2","unstructured":"\u00a0"},{"key":"e_1_2_7_59_2","doi-asserted-by":"publisher","DOI":"10.1107\/S0567740881007814"},{"key":"e_1_2_7_60_2","doi-asserted-by":"publisher","DOI":"10.1107\/S0108270195009577"},{"key":"e_1_2_7_61_2","doi-asserted-by":"publisher","DOI":"10.1016\/S0022-328X(00)82709-6"},{"key":"e_1_2_7_62_2","unstructured":"\u00a0"},{"key":"e_1_2_7_63_2","doi-asserted-by":"publisher","DOI":"10.1021\/ic50079a041"},{"key":"e_1_2_7_64_2","doi-asserted-by":"publisher","DOI":"10.1021\/om0301738"},{"key":"e_1_2_7_65_2","doi-asserted-by":"publisher","DOI":"10.1002\/cber.19851180614"},{"key":"e_1_2_7_66_2","doi-asserted-by":"publisher","DOI":"10.1021\/ja01034a067"},{"key":"e_1_2_7_67_2","doi-asserted-by":"publisher","DOI":"10.1016\/j.jorganchem.2005.10.044"},{"volume-title":"Purification of Laboratory Chemicals","year":"1996","author":"Armarego W. L. F.","key":"e_1_2_7_68_2"},{"key":"e_1_2_7_69_2","doi-asserted-by":"publisher","DOI":"10.1039\/DT9850001585"},{"key":"e_1_2_7_70_2","doi-asserted-by":"publisher","DOI":"10.1021\/jo00109a010"},{"key":"e_1_2_7_71_2","doi-asserted-by":"publisher","DOI":"10.1002\/ejic.200600551"},{"key":"e_1_2_7_72_2","doi-asserted-by":"publisher","DOI":"10.1351\/pac199971081593"},{"key":"e_1_2_7_73_2","doi-asserted-by":"publisher","DOI":"10.1107\/S0021889893002018"},{"key":"e_1_2_7_74_2","unstructured":"APEX2 Data Collection Software Version 2.1\u2010RC13 Bruker AXS Delft The Netherlands 2006."},{"key":"e_1_2_7_75_2","unstructured":"Cryopad Remote Monitoring and Control Version 1.451 Oxford Cryosystems Oxford United Kingdom 2006."},{"key":"e_1_2_7_76_2","unstructured":"SAINT+ Data Integration Engine Version 7.23a\u00a91997\u20132005 Bruker AXS Madison Wisconsin USA."},{"key":"e_1_2_7_77_2","unstructured":"G. M. Sheldrick SADABS Version 2.01 Bruker\/Siemens Area Detector Absorption Correction Program Bruker AXS Madison Wisconsin USA 1998."},{"key":"e_1_2_7_78_2","unstructured":"G. M. Sheldrick SHELXS\u201097 Program for Crystal Structure Solution University of G\u00f6ttingen 1997."},{"key":"e_1_2_7_79_2","unstructured":"G. M. Sheldrick SHELXL\u201097 Program for Crystal Structure Refinement University of G\u00f6ttingen 1997."}],"container-title":["European Journal of Inorganic Chemistry"],"original-title":[],"language":"en","link":[{"URL":"https:\/\/api.wiley.com\/onlinelibrary\/tdm\/v1\/articles\/10.1002%2Fejic.200700121","content-type":"unspecified","content-version":"vor","intended-application":"text-mining"},{"URL":"https:\/\/onlinelibrary.wiley.com\/doi\/pdf\/10.1002\/ejic.200700121","content-type":"application\/pdf","content-version":"vor","intended-application":"text-mining"},{"URL":"https:\/\/onlinelibrary.wiley.com\/doi\/full-xml\/10.1002\/ejic.200700121","content-type":"application\/xml","content-version":"vor","intended-application":"text-mining"},{"URL":"https:\/\/chemistry-europe.onlinelibrary.wiley.com\/doi\/pdf\/10.1002\/ejic.200700121","content-type":"unspecified","content-version":"vor","intended-application":"similarity-checking"}],"deposited":{"date-parts":[[2025,10,14]],"date-time":"2025-10-14T19:24:05Z","timestamp":1760469845000},"score":1,"resource":{"primary":{"URL":"https:\/\/chemistry-europe.onlinelibrary.wiley.com\/doi\/10.1002\/ejic.200700121"}},"subtitle":[],"short-title":[],"issued":{"date-parts":[[2007,6]]},"references-count":79,"journal-issue":{"issue":"18","published-print":{"date-parts":[[2007,6]]}},"alternative-id":["10.1002\/ejic.200700121"],"URL":"https:\/\/doi.org\/10.1002\/ejic.200700121","archive":["Portico"],"relation":{},"ISSN":["1434-1948","1099-0682"],"issn-type":[{"type":"print","value":"1434-1948"},{"type":"electronic","value":"1099-0682"}],"subject":[],"published":{"date-parts":[[2007,6]]},"assertion":[{"value":"2007-01-29","order":0,"name":"received","label":"Received","group":{"name":"publication_history","label":"Publication History"}},{"value":"2007-06-18","order":3,"name":"published","label":"Published","group":{"name":"publication_history","label":"Publication History"}}]}}