Abstract <p>New nickel(II) pincer complexes based on the pentamethylruthenocene, NiCl[{2,5-(R₂PCH₂)₂C₅H₂}Ru(Cp*)] (Cp* = C₅Me₅, <b>Ia</b>: R = ^<i>t</i>Bu; <b>Ib</b>: R = ^<i>i</i>Pr), were synthesized via a two-step route starting from the 1,3-functionally substituted diol {1,3-(HOCH₂)C₅H₃}Ru(Cp*). In the first step, diol was reacted with dialkylphosphines (^<i>t</i>Bu₂PH, ^<i>i</i>Pr₂PH) in acetic acid to give diphosphines{1,3-(R₂PCH₂)₂C₅H₃}Ru(Cp*) (R <b>=</b> ^<i>t</i>Bu; ^<i>i</i>Pr), which were not isolated in a pure state, but after the removal AcOH, was immediately subjected to cyclometallation with nickel(II) chloride hexahydrate in the presence of pyridine. After all purification procedures, the yields of products <b>Ia</b> and <b>Ib</b> were 31 and 16%, respectively. The complexes were fully characterized by ¹H, ³¹P{¹H}, and ¹³C{¹H} NMR spectroscopy data. The purity of the products was confirmed by elemental analysis. The structure of complex <b>Ia</b> was established by single crystal X-ray diffraction (CCDC no. 2408463).</p>