Abstract
A comparative theoretical study on the reactivity of the complexes [ReY(CO)3(bipy)] (Y = NH2, NHMe, NHpTol, OH, OMe, OPh, PH2, PHMe, PMe2, PHPh, PPh2, PMePh, SH, SMe, SPh; bipy = 2,2′-bipyridine) towards methyl propiolate was carried out to analyze the influence of both the heteroatom (N, O, P, S) and the alkyl and/or aryl substituents of the Y ligand on the nature of the product obtained. The methyl substituent tends to accelerate the reactions. However, an aromatic ring bonded to N and O makes the reaction more difficult, whereas its linkage to P and S favour it. On the whole, ligands with O and S heteroatoms seem to disfavour these processes more than ligands with N and P heteroatoms, respectively. Phosphido and thiolato ligands tend to yield a coupling product with the bipy ligand, which is not the general case for hydroxo, alcoxo or amido ligands. When the Y ligand has an O/N and an H atom the most likely product is the one containing a coupling with the carbonyl ligand, which is not always obtained when Y contains P/S. Only for OMe and OPh, the product resulting from formal insertion into the Re-Y bond is the preferred.
Highlights
IntroductionRhenium(I) fac-tricarbonyl complexes bearing conjugated diimine bidentate ligands (i.e., bipyridines, phenanthrolines, etc.) and neutral or anionic monodentate ligands (e.g., halides, pyridines, aqua, phosphines, alkyls, etc.) are functional molecules with applications in several important areas, such as catalytic reduction of CO2 [1,2,3,4,5,6,7,8,9,10,11,12,13,14,15,16], luminescence [17,18,19,20,21,22,23,24,25,26,27,28,29,30], medicinal chemistry [31,32,33,34,35,36,37,38,39,40,41,42,43,44,45,46], supramolecular chemistry [47], etc
As previously reported [58], apart from the HOMO energy of the reactant complex, other factors must be considered to rationalize this unexpected trend, so we reactant complex, other factors must be considered to rationalize this unexpected trend, so we focus on the availability of the attacking electron lone pair of the nucleophilic atom at the Y ligand
Gave rise to several potential energy surfaces, all of them with an initial large energy TS for the nucleophilic attack of Y to HMAD followed by diverse reaction channels towards three kinds of products, Pcco/Pccoh, Pccb, and Pins
Summary
Rhenium(I) fac-tricarbonyl complexes bearing conjugated diimine bidentate ligands (i.e., bipyridines, phenanthrolines, etc.) and neutral or anionic monodentate ligands (e.g., halides, pyridines, aqua, phosphines, alkyls, etc.) are functional molecules with applications in several important areas, such as catalytic reduction of CO2 [1,2,3,4,5,6,7,8,9,10,11,12,13,14,15,16], luminescence [17,18,19,20,21,22,23,24,25,26,27,28,29,30], medicinal chemistry [31,32,33,34,35,36,37,38,39,40,41,42,43,44,45,46], supramolecular chemistry [47], etc. (Y = alkoxo [48,49], amido [50,51], hydroxo [52], phosphido [53,54], thiolato [55]; N-N = 2,20 -bipyridine (bipy) and/or 1,10 phenanthroline (phen)). The Y ligand in these complexes bears one or more lone electron pairs. Due to their filled d6 electron configuration, the Y ligands cannot act as π-donors in these complexes (see Supporting Information for more details). Molecules 2020, 25, x FOR PEER REVIEW thiolato [55]; N-N = 2,2′-bipyridine (bipy) and/or 1,10 phenanthroline (phen)). The Y ligand in these complexes one or more lone electron pairs Due to their filled d6 electron configuration, the
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