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Catalyst speciation studies revealed rich coordination chemistry and the complexes thus formed were isolated and in turn tested as catalysts; the results underscore the importance of dinuclearity in engendering the observed\n                    <jats:italic>E<\/jats:italic>\n                    \u2010selectivity and provide insights into the nature of the active catalyst. The insertion product obtained from treating\n                    <jats:bold>2<\/jats:bold>\n                    with (cyclopropylethynyl)benzene contains a\n                    <jats:italic>cis<\/jats:italic>\n                    \u2010alkenyl bridging ligand with the cyclopropyl ring being intact. Treatment of this complex with H\n                    <jats:sub>2<\/jats:sub>\n                    affords exclusively\n                    <jats:italic>trans<\/jats:italic>\n                    \u2010(2\u2010cyclopropylvinyl)benzene. These results, in addition to other control experiments, indicate a non\u2010radical mechanism for\n                    <jats:italic>E<\/jats:italic>\n                    \u2010SASH, which is highly unusual for Mn\u2212H catalysts. The catalytically active species are virtually inactive towards\n                    <jats:italic>cis<\/jats:italic>\n                    to\n                    <jats:italic>trans<\/jats:italic>\n                    alkene isomerization indicating that the\n                    <jats:italic>E<\/jats:italic>\n                    \u2010selective process is intrinsic and dinuclear complexes play a critical role. A reaction mechanism is proposed accounting for the observed reactivity which is fully consistent with a kinetic analysis of the rate limiting step and is further supported by DFT computations.\n                  <\/jats:p>","DOI":"10.1002\/chem.202201766","type":"journal-article","created":{"date-parts":[[2022,6,13]],"date-time":"2022-06-13T10:22:38Z","timestamp":1655115758000},"update-policy":"https:\/\/doi.org\/10.1002\/crossmark_policy","source":"Crossref","is-referenced-by-count":9,"title":["Bench\u2010Stable Dinuclear Mn(I) Catalysts in\n                    <i>E<\/i>\n                    \u2010Selective Alkyne Semihydrogenation: A Mechanistic Investigation**"],"prefix":"10.1002","volume":"28","author":[{"ORCID":"https:\/\/orcid.org\/0000-0002-2283-7122","authenticated-orcid":false,"given":"Preshit C.","family":"Abhyankar","sequence":"first","affiliation":[{"name":"Department of Chemistry University at Buffalo State University of New York  Buffalo New York 14260 USA"}],"role":[{"role":"author","vocabulary":"crossref"}]},{"ORCID":"https:\/\/orcid.org\/0000-0001-6516-1823","authenticated-orcid":false,"given":"Samantha N.","family":"MacMillan","sequence":"additional","affiliation":[{"name":"Department of Chemistry and Chemical Biology Cornell University  Ithaca New York 14853 USA"}],"role":[{"role":"author","vocabulary":"crossref"}]},{"ORCID":"https:\/\/orcid.org\/0000-0001-5546-5081","authenticated-orcid":false,"given":"David C.","family":"Lacy","sequence":"additional","affiliation":[{"name":"Department of Chemistry University at Buffalo State University of New York  Buffalo New York 14260 USA"}],"role":[{"role":"author","vocabulary":"crossref"}]}],"member":"311","published-online":{"date-parts":[[2022,7,27]]},"reference":[{"key":"e_1_2_8_1_1","doi-asserted-by":"publisher","DOI":"10.1515\/znb-1962-1121"},{"key":"e_1_2_8_2_1","doi-asserted-by":"publisher","DOI":"10.1515\/znb-1963-0716"},{"key":"e_1_2_8_3_1","first-page":"851","author":"Johnson B. 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In contrast six-coordinate 18-e\u2212complexes are colorless to orange but most are yellow. Of all the complexes studied in this report only 3 exhibited the dark color typical of unsaturated Mn(I) compounds;"},{"key":"e_1_2_8_50_2","doi-asserted-by":"publisher","DOI":"10.1039\/D0DT00973C"},{"key":"e_1_2_8_51_1","unstructured":"This mechanism is commonly found for second and third row transition metals."},{"key":"e_1_2_8_52_2","doi-asserted-by":"publisher","DOI":"10.1021\/om970489d"},{"key":"e_1_2_8_53_2","doi-asserted-by":"publisher","DOI":"10.1021\/om00041a014"},{"key":"e_1_2_8_54_1","unstructured":"A significant amount of hpa was produced in the reaction with 8."},{"key":"e_1_2_8_55_1","unstructured":"Other byproducts included brown ppt that likely accounts for remaining Mn."},{"key":"e_1_2_8_56_1","doi-asserted-by":"publisher","DOI":"10.1039\/DT9870002669"},{"key":"e_1_2_8_57_1","doi-asserted-by":"publisher","DOI":"10.1021\/cr3001753"},{"key":"e_1_2_8_58_1","unstructured":"\u00a0"},{"key":"e_1_2_8_59_2","doi-asserted-by":"publisher","DOI":"10.1021\/acscatal.6b01045"},{"key":"e_1_2_8_60_2","doi-asserted-by":"publisher","DOI":"10.1246\/cl.160410"},{"key":"e_1_2_8_61_1","unstructured":"\u00a0"},{"key":"e_1_2_8_62_2","doi-asserted-by":"publisher","DOI":"10.1021\/ja00379a040"},{"key":"e_1_2_8_63_2","doi-asserted-by":"publisher","DOI":"10.1021\/ja00349a030"},{"key":"e_1_2_8_64_1","doi-asserted-by":"publisher","DOI":"10.1021\/jacs.5b10357"},{"key":"e_1_2_8_65_1","unstructured":"\u00a0"},{"key":"e_1_2_8_66_2","doi-asserted-by":"publisher","DOI":"10.1021\/jacs.8b08550"},{"key":"e_1_2_8_67_2","doi-asserted-by":"publisher","DOI":"10.1021\/acs.organomet.9b00331"},{"key":"e_1_2_8_68_1","unstructured":"Selected examples for both alkynes and alkenes:"},{"key":"e_1_2_8_69_2","doi-asserted-by":"publisher","DOI":"10.1021\/ja306120n"},{"key":"e_1_2_8_70_2","doi-asserted-by":"publisher","DOI":"10.1021\/acs.chemrev.6b00334"},{"key":"e_1_2_8_71_2","doi-asserted-by":"publisher","DOI":"10.1021\/acs.orglett.9b04594"},{"key":"e_1_2_8_72_2","doi-asserted-by":"publisher","DOI":"10.1021\/jacs.1c02629"},{"key":"e_1_2_8_73_2","doi-asserted-by":"publisher","DOI":"10.1021\/jacs.1c12043"},{"key":"e_1_2_8_74_1","unstructured":"Although a popular control reaction used to \u201crule out\u201d radical mechanisms the use of TEMPO to test for radical mechanisms should be used with caution. A positive control with TEMPO relies on"},{"key":"e_1_2_8_75_2","unstructured":"correct rate constant for TEMPO+intermediate and\/or;"},{"key":"e_1_2_8_76_2","unstructured":"that the O\u2212H bond strength is sufficiently weak to be captured by TEMPO. These may not be valid in many cases since TEMPO is sterically hindered and TEMPOH has a notably weak O\u2212H bond. 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