122768-46-1Relevant articles and documents
Synthesis and characterization of Pd(0) and Pt(0) metallocryptands encapsulating Tl+ ion
Catalano, Vincent J.,Bennett, Byron L.,Yson, Renante L.,Noll, Bruce C.
, p. 10056 - 10062 (2000)
Pt(0)/Pd(0) metallocryptates encapsulating Tl(I) have been constructed utilizing mixed phosphineimine ligands 2,9-bis(diphenylphosphino)-1,10-phenathroline, P2phen, and 6,6′-bis(diphenylphosphino)-2,2′-bipyridine, P2bpy. The red compounds [M2Tl(P2phen)3](NO3) (M = Pt, 1; M = Pd, 3) and [M2Tl(P2bpy)3](NO3) (M = Pt, 2; M = Pd, 4) have been isolated as air-stable crystalline solids. Complexes 1-4 exhibit single signals in their 205Tl NMR spectra that are well deshielded compared to the TlNO3(aq) reference signal. Additionally, 195Pt NMR spectra of complexes 1 and 2 exhibit a doublet of quartets pattern resulting from large one-bond couplings to both 31P and 205Tl. Characterization of 1-4 by single-crystal X-ray diffraction studies confirms the metallocryptand structure consisting of three phosphine-imine ligands in a D3-symmetric cage with the Tl(I) ion in its center and the zero-valent Pt or Pd atoms on each end. Each Pd or Pt atom is coordinated to three phosphorus centers, forming approximately trigonal geometry. The Tl(I) ion is positioned away from the imine nitrogen atoms of the phosphine ligands by ～3.5 A. Further, the outer capping metals are distorted toward the central Tl(I) ion, indicating a strong interaction. The Pt-Tl and Pd-Tl separations are at ～2.8 A each, further manifesting the strength of the metallophilic attraction in these assemblies.
