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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) 3 , PPh 3 , PMe 3 , PCy 3 , 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 3 )] + SnIBu 3 → [AuI(PPh 3 )] + SnRBu 3 for seven R groups have been measured and compared with those of the corresponding [AuR(PPh 3 )] protonolysis.

Comparing Protonolysis and Transmetalation Reactions: Microcalorimetric Studies of C–AuI Bonds in [AuRL] Complexes

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