{"status":"ok","message-type":"work","message-version":"1.0.0","message":{"indexed":{"date-parts":[[2025,10,8]],"date-time":"2025-10-08T13:11:11Z","timestamp":1759929071367,"version":"build-2065373602"},"reference-count":31,"publisher":"Wiley","issue":"8-9","license":[{"start":{"date-parts":[[2008,7,4]],"date-time":"2008-07-04T00:00:00Z","timestamp":1215129600000},"content-version":"vor","delay-in-days":0,"URL":"http:\/\/onlinelibrary.wiley.com\/termsAndConditions#vor"}],"content-domain":{"domain":[],"crossmark-restriction":false},"short-container-title":["Chemistry \u0097 An Asian Journal"],"published-print":{"date-parts":[[2008,9]]},"abstract":"<jats:title>Abstract<\/jats:title><jats:p>Addition of four equivalents of lithium 2,5\u2010dimethylpyrrolide to a solution of [Mo(NAr)(OR<jats:sub>F6<\/jats:sub>)<jats:sub>2<\/jats:sub>(CHC<jats:sub>5<\/jats:sub>H<jats:sub>4<\/jats:sub>)]<jats:sub>2<\/jats:sub>Fe (OR<jats:sub>F6<\/jats:sub>=OCMe(CF<jats:sub>3<\/jats:sub>)<jats:sub>2<\/jats:sub>) in dichloromethane led to [Mo(NAr)(Me<jats:sub>2<\/jats:sub>Pyr)<jats:sub>2<\/jats:sub>(CHC<jats:sub>5<\/jats:sub>H<jats:sub>4<\/jats:sub>)]<jats:sub>2<\/jats:sub>Fe (<jats:bold>2<\/jats:bold>; Me<jats:sub>2<\/jats:sub>Pyr=2,5\u2010dimethylpyrrolide) and lithium hexafluoro\u2010<jats:italic>tert<\/jats:italic>\u2010butoxide, which crystallizes out upon cooling the reaction mixture to \u221235\u2009\u00b0C. Attempts to prepare parent pyrrolide complexes analogous to <jats:bold>2<\/jats:bold> resulted in the formation of a mixture of two products. The one that could be isolated contains one equivalent of lithium pyrrolide per molybdenum, that is [Mo(NAr)(Pyr)<jats:sub>3<\/jats:sub>(CHC<jats:sub>5<\/jats:sub>H<jats:sub>4<\/jats:sub>)]<jats:sub>2<\/jats:sub>FeLi<jats:sub>2<\/jats:sub> (<jats:bold>3<\/jats:bold>). The X\u2010ray structure obtained shows it to be a dimer of dimers in which each lithium atom is bound to three pyrrolides. Addition of four equivalents of lithium 2,5\u2010dimethylpyrrolide to [Mo(NAr)(OR<jats:sub>F6<\/jats:sub>)<jats:sub>2<\/jats:sub>]<jats:sub>2<\/jats:sub>(DME)<jats:sub>2<\/jats:sub>(CH\u20101,4\u2010C<jats:sub>6<\/jats:sub>H<jats:sub>4<\/jats:sub>CH) (<jats:bold>1\u2009b<\/jats:bold>) in cold DME produced [Mo(NAr)(Me<jats:sub>2<\/jats:sub>Pyr)<jats:sub>2<\/jats:sub>]<jats:sub>2<\/jats:sub>(CH\u20101,4\u2010C<jats:sub>6<\/jats:sub>H<jats:sub>4<\/jats:sub>CH) (<jats:bold>4<\/jats:bold>) in good yield, in which the bridging alkylidene is derived from 1,4\u2010divinylbenzene. Three equivalents of (<jats:italic>S<\/jats:italic>)\u2010H<jats:sub>2<\/jats:sub>[Biphen] are required for a clean reaction with <jats:bold>3<\/jats:bold> to form [Mo(NAr)(Biphen)(CHC<jats:sub>5<\/jats:sub>H<jats:sub>4<\/jats:sub>)]<jats:sub>2<\/jats:sub>Fe (<jats:bold>5<\/jats:bold>) (H<jats:sub>2<\/jats:sub>[Biphen]=3,3\u2032\u2010di\u2010<jats:italic>tert<\/jats:italic>\u2010butyl\u20105,5\u2032,6,6\u2032\u2010tetramethyl\u20101,1\u2032\u2010biphenyl\u20102,2\u2032\u2010diol), Li<jats:sub>2<\/jats:sub>[Biphen], and two equivalents of pyrrole. Reactions involving <jats:bold>4<\/jats:bold> with the chiral diols are the best behaved. Brown [Mo(NAr)(Benz<jats:sub>2<\/jats:sub>Bitet)]<jats:sub>2<\/jats:sub>(CH\u20101,4\u2010C<jats:sub>6<\/jats:sub>H<jats:sub>4<\/jats:sub>CH) (<jats:bold>6<\/jats:bold>) can be isolated upon addition of (<jats:italic>R<\/jats:italic>)\u2010H<jats:sub>2<\/jats:sub>[Benz<jats:sub>2<\/jats:sub>Bitet] (H<jats:sub>2<\/jats:sub>[Benz<jats:sub>2<\/jats:sub>Bitet]=(3,3\u2032\u2010dibenzhydryl\u20105,5\u2032,6,6\u2032,7,7\u2032,8,8\u2032\u2010octahydro\u20101,1\u2032\u2010binaphthyl\u20102,2\u2032\u2010diol) to <jats:bold>4<\/jats:bold>, while addition of (<jats:italic>R<\/jats:italic>)\u2010H<jats:sub>2<\/jats:sub>[Mes<jats:sub>2<\/jats:sub>Bitet] (H<jats:sub>2<\/jats:sub>[Mes<jats:sub>2<\/jats:sub>Bitet]=3,3\u2032\u2010dimesityl\u20105,5\u2032,6,6\u2032,7,7\u2032,8,8\u2032\u2010octahydro\u20101,1\u2032\u2010binaphthyl\u20102,2\u2032\u2010diol) to <jats:bold>4<\/jats:bold> yields [Mo(NAr)(Mes<jats:sub>2<\/jats:sub>Bitet)]<jats:sub>2<\/jats:sub>(CH\u20101,4\u2010C<jats:sub>6<\/jats:sub>H<jats:sub>4<\/jats:sub>CH) (<jats:bold>7<\/jats:bold>). Compounds <jats:bold>5<\/jats:bold>, <jats:bold>6<\/jats:bold>, and <jats:bold>7<\/jats:bold> were employed as initiators for the polymerization of 2,3\u2010dicarbomethoxynorbornadiene (DCMNBD) and 2,3\u2010bis(trifluoromethyl)norbornadiene (NBDF6).<\/jats:p>","DOI":"10.1002\/asia.200800076","type":"journal-article","created":{"date-parts":[[2008,7,5]],"date-time":"2008-07-05T13:41:20Z","timestamp":1215265280000},"page":"1535-1543","source":"Crossref","is-referenced-by-count":7,"title":["Synthesis of Bifunctional Imido Alkylidene BisPyrrolide Complexes of Molybdenum and Their Conversion into Bifunctional Imido Alkylidene Diolate Complexes That Can Be Employed as ROMP Initiators"],"prefix":"10.1002","volume":"3","author":[{"given":"Andrea\u2005J.","family":"Gabert","sequence":"first","affiliation":[],"role":[{"role":"author","vocabulary":"crossref"}]},{"given":"Richard\u2005R.","family":"Schrock","sequence":"additional","affiliation":[],"role":[{"role":"author","vocabulary":"crossref"}]},{"given":"Peter","family":"M\u00fcller","sequence":"additional","affiliation":[],"role":[{"role":"author","vocabulary":"crossref"}]}],"member":"311","published-online":{"date-parts":[[2008,9,22]]},"reference":[{"unstructured":"\u00a0","key":"e_1_2_6_1_2"},{"volume-title":"Block Copolymers","year":"1977","author":"Noshay A.","key":"e_1_2_6_2_2"},{"volume-title":"Block Copolymers \u2010 Synthetic Strategies, Physical Properties, and Applications","year":"2003","author":"Hadjichristidis N.","key":"e_1_2_6_3_2"},{"unstructured":"\u00a0","key":"e_1_2_6_4_2"},{"doi-asserted-by":"publisher","key":"e_1_2_6_5_2","DOI":"10.1021\/ja01592a101"},{"doi-asserted-by":"publisher","key":"e_1_2_6_6_2","DOI":"10.1038\/1781168a0"},{"unstructured":"\u00a0","key":"e_1_2_6_7_2"},{"doi-asserted-by":"publisher","key":"e_1_2_6_8_2","DOI":"10.1021\/om00027a028"},{"doi-asserted-by":"publisher","key":"e_1_2_6_9_2","DOI":"10.1021\/ma00198a003"},{"doi-asserted-by":"publisher","key":"e_1_2_6_10_2","DOI":"10.1021\/ma9513426"},{"doi-asserted-by":"publisher","key":"e_1_2_6_11_2","DOI":"10.1021\/ma0524373"},{"doi-asserted-by":"publisher","key":"e_1_2_6_12_2","DOI":"10.1021\/ma052510p"},{"doi-asserted-by":"publisher","key":"e_1_2_6_13_2","DOI":"10.1021\/om058022n"},{"doi-asserted-by":"publisher","key":"e_1_2_6_14_2","DOI":"10.1021\/ma060243x"},{"doi-asserted-by":"publisher","key":"e_1_2_6_15_2","DOI":"10.1002\/ange.200300576"},{"doi-asserted-by":"publisher","key":"e_1_2_6_15_3","DOI":"10.1002\/anie.200300576"},{"doi-asserted-by":"publisher","key":"e_1_2_6_16_2","DOI":"10.1021\/ja0665904"},{"doi-asserted-by":"publisher","key":"e_1_2_6_17_2","DOI":"10.1021\/om7006985"},{"unstructured":"R. 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