Reactivity of thioesters with respect to nucleophilic attack
According to these lecture notes from Gonzaga University:


  The question arises over why thioesters occupy a prominent place in metabolism while oxygen esters play a relatively minor role. One answer is thermodynamic. The sulfur in the thioester linkage is less able to participate in electron delocalization through the acyl group (the usual explanation given for this is poor overlap between the 2p orbital of carbon and the 3p orbital of sulfur), and this makes the thioester bond less stable than the ester bond. Hence, the thioester bond has a more negative standard free energy of hydrolysis (−7.5 kcal/mole vs. about −5 kcal/mole for most oxygen esters). In many cases, it appears that thioesters are more reactive than oxygen esters, undergoing more facile nucleophilic displacement reactions at the acyl group. The reactivity of a thioester at the alpha carbon compares favorably with that of ketones.


...


  Because resonance structure 2c [see web page - CF] makes a more significant contribution for a thioester than an analogous structure for an ester, the acyl carbon is more positive, hence more susceptible to nucleophilic attack. An attacking nucleophile would be more readily acylated by a thioester than it would be by an ester. Furthermore, the C-S bond is weaker than the C-O bond, and the thiolate (or thiol, if protonated) is a better leaving group than alkoxide (or alcohol). These factors all make a thioester in general a better acylating agent than an ester.


So the answer doesn't seem to involve d orbitals explicitly, but instead the difference between 2p and 3p orbitals (as well as other factors).