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Theory‐enforced Re‐investigation of the Origin of the Large Metal–Carbon Bond Strength in PdCH 2 I + and its reactions with unsaturated hydrocarbons
Author(s) -
Schwarz Joseph,
Schröder Detlef,
Schwarz Helmut,
Heinemann Christoph,
Hrušák Jan
Publication year - 1996
Publication title -
helvetica chimica acta
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 0.74
H-Index - 82
eISSN - 1522-2675
pISSN - 0018-019X
DOI - 10.1002/hlca.19960790419
Subject(s) - chemistry , endothermic process , bond dissociation energy , dissociation (chemistry) , bond energy , ab initio , molecule , double bond , carbon fibers , computational chemistry , adsorption , organic chemistry , materials science , composite number , composite material
State‐of‐the‐art ab initio studies demonstrate that the reaction Pd + + CH 3 I → PdCH 2 I + + H . is endothermic by ca. 20 kcal/mol, which translates into a bond dissociation energy ( BDE ) of ca. 83 kcal/mol for the Pd + CH 2 I bond. This figure is in agreement with an experimental bracket of 68 kcal/mol < BDE (Pd + CH 2 I) < 92 kcal/mol. Based on these findings, the previously studied Pd + /CH 3 I system was re‐investigated, and double‐resonance experiments demonstrate that the formation of PdCH 2 I + occurs stepwise via PdCH 3 +as a reactive intermediate. Further, ion/molecule reactions of PdCH 2 I + with unsaturated hydrocarbons are studied, which reveal the formation of carbon–carbon bonds in the gas phase.