Peter L Dunn1, Evan P Beaumier1, Ian A Tonks1. 1. Department of Chemistry, University of Minnesota - Twin Cities, 207 Pleasant St SE, Minneapolis MN 55455.
Abstract
The synthesis of the metalloligand Ta(κ2-NP)3Cl2 (NP = 2-diphenylphosphinopyrrolide) and its coordination chemistry with group 9 and 10 metals is reported. Treatment of Ta(κ2-NP)3Cl2 with group 9 and 10 metals resulted in clean formation of the heterobimetallic complexes Cl2Ta(μ2-NP)3M (M = Ni (2), Pd (3)) or Cl2Ta(μ2-NP)3MCl (M = Rh (4), Ir (5)). Each pair of complexes is isostructural and contains three phosphinopyrrolide ligands that bridge the metal centers. The d10 or d8 complexes are all diamagnetic and X-ray crystallographic analysis reveals similarly short metal-metal distances, ranging from 2.2979(5) Å to 2.4366(2) Å. Despite the similar bonding metrics in 2-5, treatment with an L type donor (2,6-dimethylphenylisocyanide (CNXylyl)) reveals 3 different coordination geometries in TaNi(CNXylyl) (6), TaPd(CNXylyl) (7), and TaIr(CNXylyl) (8). While complexes 6, 7, and 8 all bind the isocyanide at the late metal, ligand rearrangements are observed in the first row complex 6. Complex 7 binds the isocyanide in the axial position while equatorial binding is observed in 8. All isocyanide adducts maintain close metal-metal contacts in the solid state.
The synthesis of the class="Chemical">metalloligand class="Chemical">pan class="Chemical">Ta(κ2-NP)3Cl2 (NP = 2-diphenylphosphinopyrrolide) and its coordination chemistry with group 9 and 10 metals is reported. Treatment of Ta(κ2-NP)3Cl2 with group 9 and 10 metals resulted in clean formation of the heterobimetallic complexes Cl2Ta(μ2-NP)3M (M = Ni (2), Pd (3)) or Cl2Ta(μ2-NP)3MCl (M = Rh (4), Ir (5)). Each pair of complexes is isostructural and contains three phosphinopyrrolide ligands that bridge the metal centers. The d10 or d8 complexes are all diamagnetic and X-ray crystallographic analysis reveals similarly short metal-metal distances, ranging from 2.2979(5) Å to 2.4366(2) Å. Despite the similar bonding metrics in 2-5, treatment with an L type donor (2,6-dimethylphenylisocyanide (CNXylyl)) reveals 3 different coordination geometries in TaNi(CNXylyl) (6), TaPd(CNXylyl) (7), and TaIr(CNXylyl) (8). While complexes 6, 7, and 8 all bind the isocyanide at the late metal, ligand rearrangements are observed in the first row complex 6. Complex 7 binds the isocyanide in the axial position while equatorial binding is observed in 8. All isocyanide adducts maintain close metal-metalcontacts in the solid state.
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