{"status":"ok","message-type":"work","message-version":"1.0.0","message":{"indexed":{"date-parts":[[2025,10,12]],"date-time":"2025-10-12T19:27:22Z","timestamp":1760297242753},"reference-count":64,"publisher":"Wiley","issue":"9","license":[{"start":{"date-parts":[[2004,9,23]],"date-time":"2004-09-23T00:00:00Z","timestamp":1095897600000},"content-version":"vor","delay-in-days":22,"URL":"http:\/\/onlinelibrary.wiley.com\/termsAndConditions#vor"}],"content-domain":{"domain":[],"crossmark-restriction":false},"short-container-title":["Chemistry &amp; Biodiversity"],"published-print":{"date-parts":[[2004,9]]},"abstract":"<jats:title>Abstract<\/jats:title><jats:p>The ability of bimetallic homo\u2010 and heteronuclear complexes of two spiro\u2010linked ligands, <jats:italic>viz.<\/jats:italic> a biazacrown (<jats:italic>i.e.<\/jats:italic>, 2,6,10,14,18,22\u2010hexaazaspiro[11.11]tricosane (<jats:bold>1<\/jats:bold>)) and an azacrown\uf8ffcrown ether (<jats:italic>i.e.<\/jats:italic>, 14,17,20,23,26\u2010pentaoxa\u20102,6,10\u2010triaza\u2010spiro[11.15]heptacosane (<jats:bold>2<\/jats:bold>)), to promote the cleavage of the phosphoester linkage of dinucleoside 3\u2032,5\u2032\u2010phosphates and the phosphoric anhydride bridge of dinucleoside 5\u2032,5\u2032\u2010triphosphates was studied. In both reactions, the bimetallic homonuclear Cu<jats:sup>2+<\/jats:sup> and Zn<jats:sup>2+<\/jats:sup> complexes were better catalysts than their monometallic counterparts. The acceleration was two\u2010 to five\u2010fold with the phosphoester cleavage and 3\u2010 to 20\u2010fold with the phosphoric anhydride cleavage. Interestingly, the most\u2010efficient catalyst of the phosphoester cleavage was the heterodinuclear Ni<jats:sup>2+<\/jats:sup>,Zn<jats:sup>2+<\/jats:sup>\u2005complex of <jats:bold>1<\/jats:bold>, the catalytic activity of which was up to 5\u2010 and 100\u2010fold that of the homodinuclear Zn<jats:sup>2+<\/jats:sup> and Ni<jats:sup>2+<\/jats:sup> complexes, respectively. Moreover, this cooperative acceleration was observed to depend on the identity of the 5\u2032\u2010linked nucleoside: 3\u2032,5\u2032\u2010UpU and 3\u2032,5\u2032\u2010ApU were cleaved much faster than 3\u2032,5\u2032\u2010UpA, and no cooperative acceleration was observed with 3\u2032,5\u2032\u2010ApA. The reaction was second\u2010order in hydroxide ion concentration, suggesting that a double deprotonation took place on going from the initial to the transition state. Evidently, in addition to deprotonation of the attacking 2\u2032\u2010OH group, N(3)H of the 5\u2032\u2010linked uridine was displaced by one of the metal ions of the cleaving agent. With the phosphoric anhydride cleavage, no similar cooperativity of two different metal ions was observed, but the greatest rate\u2010acceleration was achieved with the homodinuclear Cu<jats:sup>2+<\/jats:sup> complexes.<\/jats:p>","DOI":"10.1002\/cbdv.200490094","type":"journal-article","created":{"date-parts":[[2004,9,23]],"date-time":"2004-09-23T16:03:28Z","timestamp":1095955408000},"page":"1316-1326","source":"Crossref","is-referenced-by-count":10,"title":["Bimetallic Complexes of Spiro\u2010Azacrown Ligands as Catalysts of Phosphoester and Phosphoric Anhydride Cleavage"],"prefix":"10.1002","volume":"1","author":[{"given":"Qi","family":"Wang","sequence":"first","affiliation":[],"role":[{"role":"author","vocabulary":"crossref"}]},{"given":"Satu","family":"Mikkola","sequence":"additional","affiliation":[],"role":[{"role":"author","vocabulary":"crossref"}]},{"given":"Harri","family":"L\u00f6nnberg","sequence":"additional","affiliation":[],"role":[{"role":"author","vocabulary":"crossref"}]}],"member":"311","published-online":{"date-parts":[[2004,9,23]]},"reference":[{"key":"e_1_2_1_1_2","doi-asserted-by":"publisher","DOI":"10.1021\/cr950043b"},{"key":"e_1_2_1_1_3","doi-asserted-by":"publisher","DOI":"10.1021\/cr950042j"},{"key":"e_1_2_1_1_4","doi-asserted-by":"publisher","DOI":"10.1002\/anie.199620241"},{"key":"e_1_2_1_2_2","doi-asserted-by":"publisher","DOI":"10.1016\/S0022-2836(05)80337-7"},{"key":"e_1_2_1_2_3","doi-asserted-by":"publisher","DOI":"10.1126\/science.1707186"},{"key":"e_1_2_1_2_4","doi-asserted-by":"publisher","DOI":"10.1002\/j.1460-2075.1991.tb07917.x"},{"key":"e_1_2_1_2_5","doi-asserted-by":"publisher","DOI":"10.1039\/cs9952400055"},{"key":"e_1_2_1_3_2","doi-asserted-by":"publisher","DOI":"10.1073\/pnas.90.14.6498"},{"key":"e_1_2_1_3_3","doi-asserted-by":"publisher","DOI":"10.1016\/S0959-440X(02)00324-X"},{"key":"e_1_2_1_4_2","doi-asserted-by":"publisher","DOI":"10.1016\/S0010-8545(98)00234-3"},{"key":"e_1_2_1_4_3","unstructured":"R. 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