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Gas‐Phase Chemistry of Ethynylamine, ‐Phosphine and ‐Arsine. Structure and Stability of their Cu + and Ni + Complexes
Author(s) -
Galiano Luis,
Alcamí Manuel,
Mó Otilia,
Yáñez Manuel
Publication year - 2003
Publication title -
chemphyschem
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 1.016
H-Index - 140
eISSN - 1439-7641
pISSN - 1439-4235
DOI - 10.1002/cphc.200390011
Subject(s) - chemistry , arsine , binding energy , heteroatom , phosphine , metal , crystallography , arsenic , density functional theory , inorganic chemistry , computational chemistry , stereochemistry , ring (chemistry) , organic chemistry , physics , nuclear physics , catalysis
The Cu + and Ni + binding energies of ethynylamine, ethynylphosphine and ethynylarsine have been calculated at the B3LYP/6‐311+G(2df,2p)//B3LYP/6‐311G(d,p) level of theory. Significant differences between nitrogen‐containing and phosphorus‐ or arsenic‐containing compounds have been found regarding structural effects upon metal cation association. While for ethynylamine the global minimum of the potential energy surface corresponds to the complex in which the metal cation binds to the β‐carbon, for ethynylphosphine the most favourable process corresponds to phosphorus attachment. For ethynylarsine, the conventional π‐complex is the most stable one. This behavior resembles that found for the corresponding vinyl analogues, with the only exception being the arsenic derivative. The calculated Cu + and Ni + binding energies for attachment to the heteroatom follow a different trend, P>As>N, to that predicted for the corresponding proton affinities, P>N>As. Cu + and Ni + binding energies are almost identical when the metal cation binds to the heteroatom. However, Ni + binding energies are slightly larger than Cu + binding energies when the metal cation interacts with the CC bond.