Dedicated to the memory of Prof. Víctor Riera, a pioneer of the Spanish Organometallic Chemistry, a great teacher and a great mentor.The dipyrromethane-based chloridogermyl complexes [MCl {k 3 P,Ge,P-GeCl(pyrmP i Pr 2 ) 2 CMe 2 }] (1 M ; M = Ni, Pd; (pyrm-P i Pr 2 ) 2 CMe 2 = 5,5'-dimethyl-2,2'-bis(di-isopropylphosphanylmethyl)dipyrromethane-1,1'-diyl) reacted with one or more equivalents of LiOMe to give the monosubstituted complexes [MCl {k 3 P,Ge,P-Ge(OMe)(pyrmP i Pr 2 ) 2 CMe 2 }] (2 MÀ OMe ; M = Ni, Pd). However, analogous treatments of complexes 1 M with LiMe afforded the dimethyl complexes [MMe{k 3 P,Ge,P-GeMe(pyrmP i Pr 2 ) 2 CMe 2 }] (3 MÀ Me ; M = Ni, Pd). The monomethyl complexes [MCl{k 3 P,Ge,P-GeMe(pyrmP i Pr 2 ) 2 CMe 2 }] (2 MÀ Me ; M = Ni, Pd), which were identified as intermediates in the syntheses of 3 MÀ Me , were satisfactorily prepared by treating 3 MÀ Me with HCl. The regioselectivities of these reactions have been rationalized with DFT calculations.