Adducts of Rh2[MTPA]4 with some phosphine chalcogenides: nature of binding and ligand exchange.
Adducts of four phosphine chalcogenides with the chiral dirhodium complex ([Rh-Rh]) were investigated by variable-temperature 1H and 31P NMR spectroscopy in order to compare their properties as axial ligands. Whereas the selenide (1) and the sulfide (2) are strong ligands with electrostatic attraction and, in addition, a significant orbital (HOMO-LUMO) interaction, the phosphine oxide compounds (P=O) bind primarily via electrostatic attraction and are relatively weak donors. Moreover, the overall bond strength in these adducts depends on steric congestion around the P=O group.
Gáti
Tamás
T
Institute for General and Analytical Chemistry, Budapest University of Technology and Economics, Szent Gellért tér 4, H-1111 Budapest, Hungary.
Simon
András
A
Tóth
Gábor
G
Magiera
Damian
D
Moeller
Stefan
S
Duddeck
Helmut
H
D001665:Binding Sites; D018011:Chalcogens / Q000032:analysis / Q000737:chemistry*; D008024:Ligands; D009682:Magnetic Resonance Spectroscopy / Q000379:methods*; D010084:Oxidation-Reduction; D010720:Phosphines / Q000032:analysis / Q000737:chemistry*; D011437:Propylamines / Q000032:analysis / Q000737:chemistry*; D012238:Rhodium / Q000032:analysis / Q000737:chemistry*; D013696:Temperature
D018011:Chalcogens; D008024:Ligands; D010720:Phosphines; D011437:Propylamines; C055136:3-methylthiopropylamine; D012238:Rhodium