Abstract
A new Pd(I)-Rh(II) heterodinuclear complex, trans-(NC) 2(CH 30) 3PRh(μ-dppm) 2PdC1 ( 2a), was prepared by treatment of [(cod)RhCI] 2 with (CH 30) 3P and trans-(NC) 2Pd(dppm) 2 ( 1) (dppm = bis(diphenylphosphino)methane, cod = 1,5-cyclooctadiene) and characterized by 31P NMR spectroscopy and single-crystal X-ray structure determination. The single crystal of complex 2a is triclinic; its space group P 1( No.2); a = 15.684(6), b = 16.059(5), c = 12.274(4) A ̊ , α = 94.43(3), β = 106.55(3), γ = 87.86(3)°. The RhPd bond distance is 2.7835(5) Å. The molecular structure of this complex suggests that its formation reaction includes: (i) ligand migrations of the Cl − from the Rh center to the Pd center and the two CN − groups from the Pd center to Rh center; (ii) the intermetallic one-electron transfer indicated by the alteration from Rh(I) and Pd(II) to Rh(1I) and Pd(I) respectively; (iii) the Pd(I)Rh(II) bond formation by pairing one electron from Rh(II) with one electron from Pd(I). The differences of chemical shifts of the phosphorus atoms coordinated to the Pd center in the PdAg complexes and the PdRh complexes are discussed.
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