Three-Coordinate Pd(0) With Rare-earth Metalloligands:Synthesis,Characterization And Reactivity Studies

This dissertation studied the synthesis,characterization and reactivity of Three?Coordinate Pd(0)supported by Rare?earth Metalloligands,which included following parts:1.A series of ?-diketiminato rare earth metal amido complexes L^nacnacLn(Ph NCH₂PPh₂)₂(Ln=Y(1),Yb(2),Lu(3))were synthesized via alkane elimination reactions from their bisalkyl precusors.Complexes 1-3 were characterized by ¹H,¹³C,³¹P{¹H}NMR spectroscopy and single crystal X-ray diffraction studies.2.Three-coordinate Pd(0)complex L^nacnacLn Pd(Ph NCH₂PPh₂)₂(Ln=Y(4),Yb(5),Lu(6))was synthesized via reactions of 1-3 with(COD)Pd(CH₂Si Me₃)₂.The Pd(0)was stablizedwith only two sterically less bulky phosphines and a notable Pd?Ln dative interaction.These heterobimetallic Ln-Pd complexes were fully characterized by ¹H,¹³C,³¹P{¹H}NMR spectroscopy,UV-Vis spectroscopy and single crystal X-ray diffraction studies.3.Thereactivity of Y-Pd(4)complex toward isonitrile ^tBu NC and CO was studied.While for the former a stable product with ^tBu NC ligated on Pd(0)was isolated and characterized.In the latter reaction with CO,a remarkable Pd(0)assisted CO insertion into Y-N bond led to the formation of a novle anionic Pd(0)carbomyl with the Y(III)weakly coordinated with the carbonyl group.4.The reaction of Y-Pd complex with iodobenzene showed a remarkable double P-C bond cleavage-formation pathway within the heterobimetallic Y-Pd core.Computational studies revealed a synergetic bimetallic mechanism for these reactions.