Abstract
Lewis addition between the metalloligand [RuCp(C[triple bond]Cpy-4)(dppf)] (1) (dppf = (C(5)H(4)PPh(2))(2)Fe) and MCl(2)(CH(3)CN)(2) gives [RuCp(C[triple bond]Cpy-4)(dppf)](2)[MCl(2)] (M = Pd (2) and Pt (3)), all of which have been spectroscopically and crystallographically characterized. The mixed-metal adducts show the d(6)-d(8)-d(6) metal alignment maintained by the trans disposition of the directionally rigid 4-ethynylpyridine at the centrosymmetric square-planar metal center. Electrochemical studies of these and the related known complexes trans-[RuCl(C[triple bond]Cpy-4)(dppm)(2)] (4) and [trans-RuCl(C[triple bond]Cpy-4)(dppm)(2)](2)[MCl(2)] (dppm = Ph(2)PCH(2)PPh(2)) (M = Pd (5) and Pt (6)) suggest that the spacer-linked heterotrinuclear network is able to stabilize the oxidized Ru(III) better than the metalloligand precursor. Cubic nonlinear optical responses are also generally higher for the heterometallic complexes. The gamma(real) value of the PdRu(2) dppm complex 5 is among the largest for linear organometallic complexes.
Published Version
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