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Syntheses, Structural Characterization, and Kinetic Investigations of Metalla[3]triangulanes: Isoelectronic Nickel(0) and Copper(I) Complexes with Bicyclopropylidene (bcp) and Dicyclopropylacetylene (dcpa) as Ligands
Author(s) -
Ritz Florian J.,
Valentin Lars,
Henss Anja,
Würtele Christian,
Walter Olaf,
Kozhushkov Sergei I.,
Meijere Armin,
Schindler Siegfried
Publication year - 2021
Publication title -
european journal of organic chemistry
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 0.825
H-Index - 155
eISSN - 1099-0690
pISSN - 1434-193X
DOI - 10.1002/ejoc.202100045
Subject(s) - chemistry , nickel , copper , reactivity (psychology) , associative substitution , kinetics , transition metal , kinetic energy , reaction mechanism , stereochemistry , crystallography , catalysis , organic chemistry , alternative medicine , pathology , quantum mechanics , medicine , physics
The kinetics of the reactions between [Ni(bipy)(COD)] and bicyclopropylidene (bcp), dicyclopropylacetylene (dcpa) and 1,4‐dimethoxy‐2‐butyne (dmbu) were investigated using stopped‐flow techniques. Similar to previous studies the results support an associative mechanism (activation parameters for bcp: Δ H # =46±2 kJ ⋅ mol −1 and Δ S # =−69±8 J ⋅ mol −1 ⋅ K −1 ) and therefore allowed to postulate a more general reaction mechanism for the reaction pathway. The products, the nickel(0) complexes [Ni(bipy)(bcp)] and [Ni(bipy)(dcpa)], could be structurally characterized and the molecular structures are presented. In addition, the corresponding copper(I) complexes [Cu(bipy)(bcp)]PF 6 and [Cu(bipy)(dcpa)]PF 6 were also structurally characterized and their reactivity towards dioxygen was investigated. A detailed discussion of the structural properties and comparisons to similar literature‐known olefinic complexes with transition metals are presented.