Four new ortho-tert-butylphenyl substituted germanes (o-Bu tC6H4)3GeX (X = Br (1), H (2), Cl (3), or OH (4)) have been prepared and structurally characterized. The structures of 1-4 have been obtained and the ortho-tert-butyl substituents were found to be oriented in the same direction as the Ge-X bond in each molecule. The presence of these bulky substituents results in distortions in 1-4 from the ideal tetrahedral geometry, which was assessed by an examination of the C ipso-Ge-Cipso-Cortho torsion angles within these four compounds. The two diaryl-substituted germanes (o-Bu tC6H4)2GeBr2 (5) and Mes2GeH2 (6) have also been prepared and structurally characterized, and the absence of a third sterically encumbering aryl group alleviates a significant amount of structural strain in these compounds versus their triaryl-substituted analogues. © 2011 Elsevier B.V. All rights reserved.