A study of compounds containing platinum, silicon, aluminum, and phosphorus using X -ray crystallography

Discussed herein are the crystal structure solutions of a number of different compounds containing platinum, silicon, aluminum, and phosphorus. Acknowledging the contributions of previous crystallographers, a short introduction to crystallography is given. Continuing, the first focus of this work deals with the solution of structures that contain the main group elements silicon, aluminum, and phosphorus. The second focus of this work deals with the solution of structures that contain platinum.;The first focus begins with a short discussion of the elements aluminum, silicon, and phosphorus. The elucidation of the first x-ray structure solution, that of Al(OSiPh3)3·NH2(i -Pr), was vital to understanding the end product of a sequential series of reactions. The next five structure solutions discussed are structures of a series of heterocyclynes which have been used, for among other things, as carbon monoxide sensors. This series includes SiVi2OBET (Vi = vinyl), SiMe2OBET, Si2Me4OBET, Me 2SiOSiMe2OBET, and PO(i-Pr)OBET (OBET = 2,2′ -orthobisethynyltolane). The last two structure solutions discussed are of a bis(mesityl)phenyl silicon moiety that showed hydrogen bonding in the solid state. These compounds, with the formulas of 2,6-Mes2C 6H3(H)Si(OH)2 and 2,6-Mes2C6H 3(H)Si(Cl)2, exhibited O-H and C-H hydrogen bonding in the solid state, respectively.;The second focus begins with a short discussion of the element platinum. The first two x-ray structure solutions discussed are those of two platinum silicon compounds with noted catalytic properties, [Pt(PPr3) 2SiH(Hex)]2, and [PtH(PPr3)2SiH 2(Mes*)]. X-ray structures here were required to unambiguously determine that the silicon atoms in the dimer [Pt(PPr3)2SiH(Hex)] 2 was indeed five coordinate. Continuing the work with heterocyclynes, next four crystal structure solutions discussed are part of another series. Two structures are platinum butadiyne precursors, (dcype)Pt(C≡CC≡C-H) 2•½CH2Cl2 (dcype = 1,2-bis-(dicyclohexylphosphino)ethane) and trans-(PPr3)2Pt(C≡CC≡C-H) 2 are given. The silver salt of a platinum heterocyclyne, cyclo-{Pt(μ-C≡CC≡C)(dcype)} 4Ag4(OTf)3Cl2(NH2Et 2)•toluene, benzene was solved with difficulty. The solution of this structure indicated a need for further characterization to confirm the initial findings. Additional characterization subsequently confirmed the solved x-ray structure. A diethylammonium triflate salt was also recrystallized from the same solution as cyclo-{Pt(μ-C≡CC≡C)(dcype)}4Ag 4(OTf)3Cl2(NH2Et2)•toluene, benzene. The last structure discussed in this chapter is of a platinum ene-yne complex, (dcype)Pt(C(CH2)C≡CSiMe3)Cl that is unique because the solution was used to explain an unexpected result.