The purpose of this study was to synthesize Re-3(mu-OCH2CMe3)(3)(OCH2CMe3)(6) and to determine if it could serve as a source of Re-3(mu-OCH2CMe3)(3)(H)(OCH2CMe3)(5) by analogy to Re-3(mu-O-i-Pr)(3)(O-i-Pr)(6), a previously reported cluster that exists in solution as an equilibrium mixture with Re-3(mu-O-i-Pr)(3)(H)(O-i-Pr)(5) and acetone. The halide Re-3(mu-Cl)(3)Cl-6(TKF)(3) reacts at room temperature in THF with 9 equiv of NaOCH2CMe3 to give Re-3(mu-OCH2CMe3)(3)(OCH2CMe3)(6). An X-ray crystallographic study shows that the core of the homoleptic cluster has virtual D-3h symmetry, which is consistent with solution NMR data. In refluxing THF, Re-3(mu-Cl)(3)Cl-6(THF)(3) reacts with 10 equiv of NaOCH2CMe3 to give [Na(THF)(2)][Re-3(mu-OCH2CMe3)(3)(H)(OCH2CMe3)(6)]. The same anionic hydride cluster is also produced when Re-3(mu-OCH2CMe3)(3)(OCH2CMe3)(6) reacts with excess NaOCH2CMe3 in hot THF. Spectroscopic and X-ray crystallographic data show that [Re-3(mu-OCH2CMe3)(3)(H)(OCH2CMe3)(6)](-) has virtual C-s core symmetry with a terminal hydride and two terminal alkoxides located at the unique rhenium atom. The hydride and one of the alkoxides have a trans H-Re-OR arrangement, and in the solid state structure the terminal alkoxide ligands at the unique rhenium atom interact with [Na(THF)(2)](+). It is proposed [Na(THF)(2)][Re-3(mu-OCH2CMe3)(3)(H)(OCH2CMe3)(6)] forms when Re-3(mu-OCH2CMe3)(3)(H)(OCH2CMe3)(5) Or its pivaldehyde adduct, which is generated by neopentoxide beta-hydrogen elimination from Re-3(mu-OCH2CMe3)(3)(OCH2CMe3)(6), is trapped by NaOCH2CMe3. Crystal data are as follows. C45H99O9Re3 at -50 degrees C : Pbca (orthorhombic); a = 19.570(2), b = 28.192(3), c = 21.203(3) Angstrom; Z = 8. Na+[C45H100O9Re3](-).2C(4)H(8)O at -50 degrees C : P1 (triclinic); a = 13.040(2), b = 14.716(2), c = 19.653(4) Angstrom; alpha = 92.38(1), beta = 92.30(1), gamma 113.42(1)degrees; Z = 2.