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Azidophosphonamido Rhodium(I) and Iridium(I) Complexes: Synthesis, Properties, and Linkage Isomerism
Emily L Trew1, Daisy E Cruz-Milette1, Douglas Turnbull1
1Department of Chemistry and Biochemistry, University of Lethbridge, Lethbridge, Canada.
Abstract:
A series of azidophosphonamido rhodium(I) and iridium(I) complexes ([iPr2P(N3R)NR]MLx; M = Rh, Ir; R = 1-adamantyl (Ad), mesityl (Mes); L = cyclooctadiene (COD), x = 1, cyclooctene (COE), x = 2, CO, x = 2) were prepared, and their stability and reactivity investigated. In the 1,5-cyclooctadiene (L = COD) complexes, the azidophosphonamido ligands coordinate in a κ2-N,Nα fashion, in which the PN3 moiety adopts a transoid conformation. Irradiation (λ = 365 nm) resulted in linkage isomerization to the κ2-N,Nβ isomers without loss of N2. Substitution of the COD co-ligands with CO in the κ2-N,Nα complexes occurred with retention of the transoid conformation in the solid state. Meanwhile, in the analogous bis(cyclooctene)rhodium(I) complex, [κ2-N,Nα-iPr2P(N3Mes)(NMes)]Rh(COE)2, the κ2-N,Nα-coordinated azidophosphonamido ligand exhibited a cisoid conformation, the first example of a stable cisoid phosphazide in the coordination sphere of a group 9 transition metal. Unlike the COD complexes, irradiation of this species resulted in N2 extrusion, yielding an iminophosphonamide, [κ2-N,N-iPr2P(NMes)2]Rh(COE)2. These complexes have been characterized by multinuclear NMR spectroscopy and single-crystal X-ray diffraction studies.
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