2026-05-05T21:54:33Zhttps://uvadoc.uva.es/oai/request

oai:uvadoc.uva.es:10324/460992021-11-04T09:05:15Zcom_10324_1186com_10324_931com_10324_894com_10324_28542com_10324_952col_10324_1404col_10324_28543

00925njm 22002777a 4500 dc Toledo Pérez, Alberto author Salamanca Verdugo, Vanesa author Pérez Moro, Teresa author Albéniz Jiménez, Ana Carmen author 2021 The transmetalation of acyclic monoamino and alkoxo carbenes from tungsten to group 11 metals has been studied for all three metals by analyzing the new metal carbenes formed and also their decomposition products in solution. The ease of transmetalation follows the trend: Au > Cu > Ag and the gold carbenes can be isolated, a copper carbene could be detected but we found no experi- mental evidence of the formation of any silver carbene. The electrophilic character of copper and gold carbenes is supported by the identity of the products formed upon hydrolysis of the carbenes involved. Silver shows a distinct behavior and the presence of Ag+ ions in an ace- tonitrile solution of a tungsten aminocarbene leads to the formal protonation of the carbene fragment to give an iminium salt. This outcome, a seemingly nucleophillic behavior, is unexpected for group 11 carbenes but DFT calculations show that tive cationic silver carbene is energetically accessible. Organometallics 2021, 40, 38-47 0276-7333 http://uvadoc.uva.es/handle/10324/46099 10.1021/acs.organomet.0c00675 38 1 47 Organometallics 40 1520-6041 Química Transmetalation of Acyclic Tungsten Carbenes to Coinage Metals: Distinct Behavior of Silver toward Carbene Transfer and Hydrolysis