{"status":"ok","message-type":"work","message-version":"1.0.0","message":{"indexed":{"date-parts":[[2026,8,25]],"date-time":"2026-08-25T10:16:47Z","timestamp":1787653007555,"version":"build-2736575974"},"reference-count":79,"publisher":"Wiley","issue":"26","license":[{"start":{"date-parts":[[2007,7,3]],"date-time":"2007-07-03T00:00:00Z","timestamp":1183420800000},"content-version":"vor","delay-in-days":0,"URL":"http:\/\/onlinelibrary.wiley.com\/termsAndConditions#vor"}],"content-domain":{"domain":[],"crossmark-restriction":false},"short-container-title":["Chemistry A European J"],"published-print":{"date-parts":[[2007,9,7]]},"abstract":"<jats:title>Abstract<\/jats:title><jats:p>The PCP\u2010Rh<jats:sup>I<\/jats:sup> complex <jats:bold>1\u2009a<\/jats:bold> based on the [1,3\u2010phenylenebis(methylene)]bis(diisopropylphosphine) ligand reacts with [diazo(phenyl)methyl]trimethylstannane (<jats:bold>2<\/jats:bold>) at room temperature to give novel pincer\u2010type phenyl(dimethylstannyl)methylene]hydrazinato complex <jats:bold>3\u2009a<\/jats:bold>. The reaction sequence involves a unique combination of Sn\uf8ffC bond cleavage, C\uf8ffC bond formation, C\uf8ffH activation and intramolecular deprotonation of a rhodium hydride intermediate, which results in methylene transfer from an SnMe group to the pincer system and PCP\u2010chelate expansion. A methylene\u2010transfer reaction was also demonstrated with tetramethyltin as the methylene source in the presence of KOC(CH<jats:sub>3<\/jats:sub>)<jats:sub>3<\/jats:sub> at room temperature. The resulting unstable \u201cchelate\u2010expanded\u201d Rh<jats:sup>I<\/jats:sup> complex [(C<jats:sub>10<\/jats:sub>H<jats:sub>5<\/jats:sub>(CH<jats:sub>2<\/jats:sub>P<jats:italic>i<\/jats:italic>Pr<jats:sub>2<\/jats:sub>)<jats:sub>2<\/jats:sub>)(CH<jats:sub>2<\/jats:sub>)Rh(L)] (L=N<jats:sub>2<\/jats:sub>, THF; <jats:bold>4\u2009a<\/jats:bold>) was isolated as its carbonyl derivative <jats:bold>5\u2009a<\/jats:bold>. Heating <jats:bold>4\u2009a<\/jats:bold> in benzene yielded an equimolar amount of toluene and <jats:bold>1\u2009a<\/jats:bold>, which demonstrates the ability of the Rh<jats:sup>I<\/jats:sup> pincer complex to extract a methylene group from an unactivated alkyl tin substrate and transfer it, via C\uf8ffC followed by C\uf8ffH activation, to an arene. Use of fluorobenzene resulted in formation of fluorotoluene. Catalytic methylene\u2010group transfer mediated by <jats:bold>1\u2009a<\/jats:bold> was not possible, because of formation of <jats:italic>o<\/jats:italic>\u2010xylylene complex <jats:bold>8<\/jats:bold> under the reaction conditions. Steric parameters play a decisive role in the reactivity with tin compounds; while <jats:italic>i<\/jats:italic>PrP derivative <jats:bold>1\u2009a<\/jats:bold> underwent facile reactions, <jats:italic>t<\/jats:italic>BuP complex <jats:bold>1\u2009b<\/jats:bold> was inert.<\/jats:p>","DOI":"10.1002\/chem.200700320","type":"journal-article","created":{"date-parts":[[2007,7,3]],"date-time":"2007-07-03T10:57:37Z","timestamp":1183460257000},"page":"7501-7509","source":"Crossref","is-referenced-by-count":19,"title":["Methylene Transfer from SnMe Groups Mediated by a Rhodium(I) Pincer Complex: Sn\uf8ffC, C\uf8ffC, and C\uf8ffH Bond Activation"],"prefix":"10.1002","volume":"13","author":[{"given":"Christian\u2005M.","family":"Frech","sequence":"first","affiliation":[],"role":[{"vocabulary":"crossref","role":"author"}]},{"given":"Linda\u2005J.\u2005W.","family":"Shimon","sequence":"additional","affiliation":[],"role":[{"vocabulary":"crossref","role":"author"}]},{"given":"David","family":"Milstein","sequence":"additional","affiliation":[],"role":[{"vocabulary":"crossref","role":"author"}]}],"member":"311","published-online":{"date-parts":[[2007,8,29]]},"reference":[{"key":"e_1_2_6_1_2","unstructured":"\u00a0"},{"key":"e_1_2_6_2_2","doi-asserted-by":"publisher","DOI":"10.1038\/370042a0"},{"key":"e_1_2_6_3_2","doi-asserted-by":"publisher","DOI":"10.1039\/cc9960002167"},{"key":"e_1_2_6_4_2","doi-asserted-by":"publisher","DOI":"10.1021\/om990282f"},{"key":"e_1_2_6_5_2","doi-asserted-by":"publisher","DOI":"10.1039\/a800537k"},{"key":"e_1_2_6_6_2","doi-asserted-by":"publisher","DOI":"10.1002\/(SICI)1521-3757(19990401)111:7<918::AID-ANGE918>3.0.CO;2-X"},{"key":"e_1_2_6_6_3","doi-asserted-by":"publisher","DOI":"10.1002\/(SICI)1521-3773(19990401)38:7<870::AID-ANIE870>3.0.CO;2-3"},{"key":"e_1_2_6_7_2","doi-asserted-by":"publisher","DOI":"10.1021\/cr960118r"},{"key":"e_1_2_6_8_2","first-page":"70","volume-title":"ACS Symposium Series, Vol.\u2005885","author":"Rybtchinski B.","year":"2004"},{"key":"e_1_2_6_9_2","unstructured":"\u00a0"},{"key":"e_1_2_6_10_2","doi-asserted-by":"publisher","DOI":"10.1021\/ja000157r"},{"key":"e_1_2_6_11_2","doi-asserted-by":"publisher","DOI":"10.1021\/om049848c"},{"key":"e_1_2_6_12_2","doi-asserted-by":"publisher","DOI":"10.1021\/ja0615066"},{"key":"e_1_2_6_13_2","unstructured":"\u00a0"},{"key":"e_1_2_6_14_2","doi-asserted-by":"publisher","DOI":"10.1016\/S0022-328X(99)00408-8"},{"key":"e_1_2_6_15_2","doi-asserted-by":"publisher","DOI":"10.1002\/cber.19911241006"},{"key":"e_1_2_6_16_2","doi-asserted-by":"publisher","DOI":"10.1016\/0022-328X(85)88083-9"},{"key":"e_1_2_6_17_2","doi-asserted-by":"publisher","DOI":"10.1021\/om060002d"},{"key":"e_1_2_6_18_2","doi-asserted-by":"publisher","DOI":"10.1021\/om0303449"},{"key":"e_1_2_6_19_2","doi-asserted-by":"publisher","DOI":"10.1016\/S0022-328X(98)00912-7"},{"key":"e_1_2_6_20_2","doi-asserted-by":"publisher","DOI":"10.1021\/om00046a003"},{"key":"e_1_2_6_21_2","doi-asserted-by":"publisher","DOI":"10.1002\/cber.19911241006"},{"key":"e_1_2_6_22_2","doi-asserted-by":"publisher","DOI":"10.1016\/S0022-328X(00)84170-4"},{"key":"e_1_2_6_23_2","unstructured":"For examples of methyl\u2010transfer reactions with Sn(CH3)4as methyl source see:"},{"key":"e_1_2_6_24_2","first-page":"1133","volume":"90","author":"Heck R. 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