{"status":"ok","message-type":"work","message-version":"1.0.0","message":{"indexed":{"date-parts":[[2026,2,1]],"date-time":"2026-02-01T06:31:21Z","timestamp":1769927481465,"version":"3.49.0"},"reference-count":42,"publisher":"Wiley","issue":"40","license":[{"start":{"date-parts":[[2011,8,23]],"date-time":"2011-08-23T00:00:00Z","timestamp":1314057600000},"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":[[2011,9,26]]},"abstract":"<jats:title>Abstract<\/jats:title><jats:p>Group\u200512 and silver(I) tetramethyl\u2010<jats:italic>m<\/jats:italic>\u2010benziporphodimethene (TMBPDM) complexes with phenyl, methylbenzoate, or nitrophenyl groups as <jats:italic>meso<\/jats:italic> substituents were synthesized and fully characterized. The dimeric silver(I) complex displays an unusual \u03b7<jats:sup>2<\/jats:sup>,\u03c0 coordination from the \u03b2\u2010pyrrolic C\uf8feC bond to the silver ion. All of the complexes displayed a close contact between the metal ion and the inner C(22)\uf8ffH(22) on the <jats:italic>m<\/jats:italic>\u2010phenylene ring. The downfield chemical shifts of H(22) and large coupling constants between Cd<jats:sup>II<\/jats:sup> and H(22) strongly support the presence of an agostic interaction between the metal ion and inner C(22)\u2013H(22). Crystal structures revealed that the <jats:italic>syn<\/jats:italic> form is the predominant conformation for TMBPDM complexes. This is distinctively different from the exclusive <jats:italic>anti<\/jats:italic> conformation observed in <jats:italic>m<\/jats:italic>\u2010benziporphyrin and tetraphenyl\u2010<jats:italic>m<\/jats:italic>\u2010benziporphodimethene (TPBPDM) complexes. Evidently, intramolecular hydrogen\u2010bonding interactions between axial chloride and methyl groups stabilize <jats:italic>syn<\/jats:italic> conformations. Unlike the merely <jats:italic>syn<\/jats:italic> conformation observed in the solid\u2010state structures of TMBPDM complexes that contain an axial chloride, in solution these complexes display highly solvent\u2010 and temperature\u2010dependent <jats:italic>syn<\/jats:italic>\/<jats:italic>anti<\/jats:italic> ratio changes. The observation of dynamic <jats:sup>1<\/jats:sup>H\u2005NMR spectroscopic scrambling between <jats:italic>syn<\/jats:italic> and <jats:italic>anti<\/jats:italic> conformations from the titration of chloride ion into the solution of the TMBPDM complex suggests that axial ligand exchange is a likely pathway for the conversion between <jats:italic>syn<\/jats:italic> and <jats:italic>anti<\/jats:italic> forms. Theoretical calculations revealed that intermolecular hydrogen\u2010bonding interactions between the axial chloride and CHCl<jats:sub>3<\/jats:sub> stabilizes the <jats:italic>anti<\/jats:italic> conformation, which explains the increased ratio for the <jats:italic>anti<\/jats:italic> form when dichloromethane or chloroform was used as the solvent.<\/jats:p>","DOI":"10.1002\/chem.201100780","type":"journal-article","created":{"date-parts":[[2011,8,31]],"date-time":"2011-08-31T18:07:29Z","timestamp":1314814049000},"page":"11332-11343","source":"Crossref","is-referenced-by-count":25,"title":["Factors That Regulate the Conformation of <i>m<\/i>\u2010Benziporphodimethene Complexes: Agostic Metal\u2013Arene Interaction, Hydrogen Bonding, and \u03b7<sup>2<\/sup>,\u03c0 Coordination"],"prefix":"10.1002","volume":"17","author":[{"given":"Gao\u2010Fong","family":"Chang","sequence":"first","affiliation":[],"role":[{"role":"author","vocabulary":"crossref"}]},{"given":"Chun\u2010Hung","family":"Wang","sequence":"additional","affiliation":[],"role":[{"role":"author","vocabulary":"crossref"}]},{"given":"Hung\u2010Chieh","family":"Lu","sequence":"additional","affiliation":[],"role":[{"role":"author","vocabulary":"crossref"}]},{"given":"Lou\u2010Sing","family":"Kan","sequence":"additional","affiliation":[],"role":[{"role":"author","vocabulary":"crossref"}]},{"given":"Ito","family":"Chao","sequence":"additional","affiliation":[],"role":[{"role":"author","vocabulary":"crossref"}]},{"given":"Wei Hao","family":"Chen","sequence":"additional","affiliation":[],"role":[{"role":"author","vocabulary":"crossref"}]},{"given":"Anil","family":"Kumar","sequence":"additional","affiliation":[],"role":[{"role":"author","vocabulary":"crossref"}]},{"given":"Liyang","family":"Lo","sequence":"additional","affiliation":[],"role":[{"role":"author","vocabulary":"crossref"}]},{"given":"Mira Anne C.","family":"dela\u2005Rosa","sequence":"additional","affiliation":[],"role":[{"role":"author","vocabulary":"crossref"}]},{"given":"Chen\u2010Hsiung","family":"Hung","sequence":"additional","affiliation":[],"role":[{"role":"author","vocabulary":"crossref"}]}],"member":"311","published-online":{"date-parts":[[2011,8,23]]},"reference":[{"key":"e_1_2_6_1_2","doi-asserted-by":"publisher","DOI":"10.1038\/417507a"},{"key":"e_1_2_6_2_2","doi-asserted-by":"publisher","DOI":"10.1016\/0022-328X(83)85065-7"},{"key":"e_1_2_6_3_2","doi-asserted-by":"publisher","DOI":"10.1073\/pnas.0610747104"},{"key":"e_1_2_6_4_2","doi-asserted-by":"publisher","DOI":"10.1016\/j.ccr.2008.07.007"},{"key":"e_1_2_6_5_2","doi-asserted-by":"publisher","DOI":"10.1021\/cr960118r"},{"key":"e_1_2_6_6_2","doi-asserted-by":"publisher","DOI":"10.1002\/ange.200604357"},{"key":"e_1_2_6_6_3","doi-asserted-by":"publisher","DOI":"10.1002\/anie.200604357"},{"key":"e_1_2_6_7_2","doi-asserted-by":"publisher","DOI":"10.1002\/chem.200304972"},{"key":"e_1_2_6_8_2","doi-asserted-by":"publisher","DOI":"10.1021\/ja039384u"},{"key":"e_1_2_6_9_2","doi-asserted-by":"publisher","DOI":"10.1021\/ic025573m"},{"key":"e_1_2_6_10_2","doi-asserted-by":"publisher","DOI":"10.1021\/ja017852z"},{"key":"e_1_2_6_11_2","doi-asserted-by":"publisher","DOI":"10.1039\/b202679a"},{"key":"e_1_2_6_12_2","doi-asserted-by":"publisher","DOI":"10.1021\/ic0155333"},{"key":"e_1_2_6_13_2","doi-asserted-by":"publisher","DOI":"10.1021\/ic034886u"},{"key":"e_1_2_6_14_2","doi-asserted-by":"publisher","DOI":"10.1021\/ic7018378"},{"key":"e_1_2_6_15_2","doi-asserted-by":"publisher","DOI":"10.1002\/ejic.200701072"},{"key":"e_1_2_6_16_2","doi-asserted-by":"publisher","DOI":"10.1021\/ja039792y"},{"key":"e_1_2_6_17_2","doi-asserted-by":"publisher","DOI":"10.1021\/ja901796j"},{"key":"e_1_2_6_18_2","doi-asserted-by":"publisher","DOI":"10.1021\/ic049172d"},{"key":"e_1_2_6_19_2","first-page":"257","volume-title":"The Porphyrin Handbook, Vol.\u20056","author":"Sessler J. 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