Synthesis and structures of germanium(II) fluorides and hydrides

Treatment of [{HC(CMeNAr)(2)}GeCl] (Ar = 2,6-iPr(2)C(6)H(3) (1), 2,6-Me2C6H3 (2)) with Me-3-SnF in dichloromethane at room temperature afforded the corresponding fluoride [{HC(CMeNAr)(2)}GeF] (Ar = 2,6-iPr(2)C(6)H(3) (3), 2,6-Me2C6H3 (4)), while with NaBH4 in THF under reflux for 12 h gave the hydride [{HC(CMeNAr)(2)}GeH(BH3)] (Ar = 2,6-iPr(2)C(6)H(3) (5), 2,6-Me2C6H3 (6)). Reaction of 3 with Me3SiN3 in toluene provided [{HC(CMeNAr)(2)}Ge(F)NSiMe3] (Ar = 2,6-iPr(2)C(6)H(3) (7)). The BH3 in 5 can be removed with Me3P to afford [{HC(CMeNAr)(2)}-GeH] (Ar = 2,6-iPr(2)C(6)H(3) (8)), Treatment of 5 with tBuLi in diethyl ether led to [{HC(C(CH2)-NAr)CMeNAr}Ge(H)BH3]Li(Et2O)(3) (Ar = 2,6-iPr(2)C(6)H(3) (9)), in which a hydrogen of one of the Me groups was eliminated, and this consequently resulted in the formation of a methylene group. Compounds 3-6 are the first examples of structurally characterized germanium(II) fluorides and hydrides. Single-crystal X-ray structural analyses indicate that compounds 3, 5, and 9 are monomeric and the germanium center resides in a trigonal-pyramidal environment in 3 and in distorted-tetrahedral environments in 5 and 9.