We report both the stepwise and one-pot syntheses of Pt(II)-Cu(I) hetero-dinuclear complexes using 4,5-diazafluorenide (L(-)) and 9-(2-(diphenylphosphino)ethyl)-4,5-diazafluorenide (L(p)(-)) as binucleating ligands. In the case of L(p)(-), the tethered phosphine arm helps anchor the Pt(II) centre onto the carbon site of the diazafluorenide and the Cu(I) centre is bound to the N,N-chelate site. In the case of L(-), the Cu(I) centre is bound to the carbon site of diazafluorenide and the Pt(II) centre is coordinated to the N,N-chelate site.

We report the synthesis and characterization of a phosphine-functionalized 4,5-diazafluorene ligand, 9-(2-(diphenylphosphino)ethyl)-4,5-diazafluorene (L p H), and its Cu(IPr) complex (IPr = N,N′-bis(2,6-diisopropylphenyl)imidazol-2-ylidene) [Cu(IPr)L p ] (2a), which exhibits a monomeric structure in solution but dimerizes in the solid state. Compound 2a reacts with Rh(PPh 3 ) 3 Cl, [Rh(COD)-Cl] 2 , Au(SMe 2 )Cl, and Au(IPr)Cl to form the macrocyclic complexes [Rh(PPh 3 )L p ] 2 (2b), [Rh(COD)L p ] 2 (2c), and [AuL p ] 2 (2d) and the mononuclear complex [Au(IPr)L p ] (2f), respectively, via ligand transfer. Although 2b−d,f could also be synthesized from the deprotonated ligand L p − and the corresponding metal starting materials directly, the reactions require longer time and give lower yields. The reaction between L p H and Au(SMe 2 )Cl gives Au(L p H) 2 Cl (2e) exclusively.