Reactions of LGeCl (L = CH[C(Me)N(Ar)](2); Ar = 2,6-iPr(2)C(6)H(3)) with KOtBu or LiR (R = 2-thienyl, N(H)Ar, PPh2) yielded the germanium(II) compounds LGeR [R = OtBu (1), 2-thienyl (2), N(H)Ar (3), PPh2 (4)]. The reduction of (2-thienyl)(2)PCl with lithium afforded the diphosphane [(2-thienyl)(2)P](2) (5). The treatment of (2-thienyl)(2)PCl with LiAlH4 or KHBtBu(3) led to the formation of (2-thienyl)(2)PH (6). The NHC-assisted reaction of LGeCl and 6 resulted in the isolation of LGeP(2-thienyl)(2) (7). This is the first example where NHC is used for eliminating HCl from compounds with P-H and Ge-Cl bonds. All solid products were characterized by elemental analysis, NMR and IR spectroscopy, and single-crystal X-ray structure determination.