Synthesis and Fundamental Properties of Stable Ph3SnSiH3 and Ph3SnGeH3 Hydrides: Model Compounds for the Design of Si−Ge−Sn Photonic Alloys

Abstract

The compounds Ph(3)SnSiH(3) and Ph(3)SnGeH(3) (Ph = C(6)H(5)) have been synthesized as colorless solids containing Sn-MH(3) (M = Si, Ge) moieties that are stable in air despite the presence of multiple and highly reactive Si-H and Ge-H bonds. These molecules are of interest since they represent potential model compounds for the design of new classes of IR semiconductors in the Si-Ge-Sn system. Their unexpected stability and high solubility also makes them a safe, convenient, and potentially useful delivery source of -SiH(3) and -GeH(3) ligands in molecular synthesis. The structure and composition of both compounds has been determined by chemical analysis and a range of spectroscopic methods including multinuclear NMR. Single crystal X-ray structures were determined and indicated that both compounds condense in a Z = 2 triclinic (P1) space group with lattice parameters (a = 9.7754(4) A, b = 9.8008(4) A, c = 10.4093(5) A, alpha = 73.35(10)(o), beta = 65.39(10)(o), gamma = 73.18(10)(o)) for Ph(3)SnSiH(3) and (a = 9.7927(2) A, b = 9.8005(2) A, c = 10.4224(2) A, alpha = 74.01(3)(o), beta = 65.48(3)(o), gamma = 73.43(3)(o)) for Ph(3)SnGeH(3). First principles density functional theory simulations are used to corroborate the molecular structures of Ph(3)SnSiH(3) and Ph(3)SnGeH(3), gain valuable insight into the relative stability of the two compounds, and provide correlations between the Si-Sn and Ge-Sn bonds in the molecules and those in tetrahedral Si-Ge-Sn solids.