Covalent attachment of one and two NP moieties to a ferrocenyl unit provides organometallic ligands 1,8-naphthyrid-2-yl-ferrocene (FcNP) and 1,1 '-bis(1,8-naphthyrid-2-yl)ferrocene (FcNP(2)). Coordination of FcNP to transition metal ions Fe '', Cu '', Zn '', and Cdii provides [FeCl2(kN(8)-FcNP)(2)] (1), [Cu(kN(8)-FcNP)(2)(NO3)(2)] (2), [Zn(kN(8)-FcNP)(4)][OTf](2) (3), and [Cd(kN(8-)FcNP)(2)(k(2)N(1),N-8-FcNP)(2)][BF4](2) (4), respectively. Dirhodium(II) compound [Rh-2(mu-FcNP)(2)(mu-O2CCH3)(2)(H2O)][OTf](2) (5) is isolated when acetonitrile-solvated [Rh-2(mu-O2CCH3)(2)](2+) is employed as a precursor. Diverse bonding modes of the NP unit, including monodentate, bidentate chelating, or binuclear bridging, are revealed in these FcNP clusters. Metallamacrocycles [M-2(FcNP(2))(2)][X](2) (M=Cu, X=CIO4 (6); M=Ag, X=OTf (7)), [PdCl2(FcNP(2))] (8), and [ZnCl2(FcNP(2))](4) (10) are obtained by the reaction of CUCIO4, AgOTf, Pd(C6H5CN)(2)CI2, and ZnCl2 with FcNP(2) in 1:1 ratios. Treatment of Cu ' and FcNP(2) in a 2:1 ratio provides [Cu-2(FcNP(2))][CIO4](2) (9). Molecular structures of compounds 1-10 have been determined by X-ray diffraction studies. Interconversion between 1:1 dimer 6 and 2:1 dimer 9 occurs by the addition of a requisite amount of Cu ' or FcNP(2). ESI-MS experiments reveal that the predominant species is the 1:1 complex {Cu(FcNP(2))}(1+) in solution for both 6 and 9. Synthesis, structures, mass spectroscopy, and electrochemistry of the transition metal compounds of FcNP and FcNP(2) are discussed.