Comparing Protonolysis and Transmetalation Reactions: Microcalorimetric Studies of C-Au I Bonds in [AuRL] Complexes

The protonolysis of C-Au bonds in [AuRL] organometallic complexes has been studied by calorimetry for 12 R groups. The experimental data have been combined with density functional theory calculations to obtain bond dissociation energy (BDE) values. The C-Au BDE values show a good correlation with th...

Full description

Saved in:
Bibliographic Details
Published in:Inorganic chemistry 2018-09, Vol.57 (17), p.11193-11200
Main Authors: Pérez-Iglesias, María, Espinet, Pablo, Casares, Juan A
Format: Article
Language:English
Citations: Items that this one cites
Items that cite this one
Online Access:Get full text
Tags: Add Tag
No Tags, Be the first to tag this record!
Description
Summary:The protonolysis of C-Au bonds in [AuRL] organometallic complexes has been studied by calorimetry for 12 R groups. The experimental data have been combined with density functional theory calculations to obtain bond dissociation energy (BDE) values. The C-Au BDE values show a good correlation with the corresponding isolobal C-H BDE values. The heat released in the protonolysis of [AuRL] has also been measured for R = Ph and L = P(OPh) , PPh , PMe , PCy , and IPr, and these values strongly depend on the trans influence of L because of the mutual destabilization of the L-Au and Au-C bonds. The enthalpies of the transmetalation reaction [AuR(PPh )] + SnIBu → [AuI(PPh )] + SnRBu for seven R groups have been measured and compared with those of the corresponding [AuR(PPh )] protonolysis.
ISSN:0020-1669
1520-510X
DOI:10.1021/acs.inorgchem.8b01758