Chemistry Commons^™

Exploring The Synthesis, Structure, And Reactivity Of Phosphorus-Chalcogen Heterocycles, Cameron Graham

Electronic Thesis and Dissertation Repository

In recent years, the field of low-coordinate main group chemistry has seen significant research interest due to their unique structures and unprecedented reactivity. Conversely, the area of phosphinidene chalcogenides, a low-coordinate phosphorus and chalcogen species, have yet to be thoroughly explored. In this context, this dissertation describes the synthesis of a number of phosphorus-chalcogen heterocycles that can be degraded to provide stoichiometric access to low-coordinate phosphorus species. The ability for successful P-Ch transfer relies on using a bulky m-terphenyl group at phosphorus that provides enough steric bulk to kinetically stabilize the phosphorus centre, but also accommodating enough to allow …

Synthesis Of Manganese(Ii) Containing Metal Chalcogen Cluster Complexes From Metal Trimethylsilylthiolate Precursors, Kyle Nw Rozic

Electronic Thesis and Dissertation Repository

The manganese(II)‐palladium(II)‐sulfide complex [MnCl₂(μ₃‐S)₂Pd₂(dppp)₂] 2 has been isolated from the reaction of [(dppp)PdCl₂] with [Li(N,N’‐tmeda)]₂[Mn(SSiMe₃)₄] 1 in a 2:1 ratio under mild conditions. The trimethylsilyl thiolate complex [(dppp)Pd(SSiMe₃)₂] 3 has been synthesized from the reaction of [(dppp)PdCl₂] with Li[SSiMe₃] as well as the reaction of [(dppp)Pd(OAc)₂] with Li[SSiMe₃] under mild conditions. The newly synthesized complex [(dppp)Pd(SSiMe₃)₂] 3 was used in reaction with the manganese(II) salt [(CH …

Bidentate Ferrocenyl-Dithiol Reagents For Nanocluster Surface Functionalization, Yiyi Liu

Electronic Thesis and Dissertation Repository

Previous work using monodentate ferrocenyl-chalcogen reagents for nanocluster surface functionalization has indicated an effective way to involve ferrocene moieties onto the surface of these frameworks. However, the abilities of the large polynuclear nanocluster with ferrocene rich surface to form crystalline materials suitable for single crystal X-ray analysis proved to be limited. New bidentate ferrocenyl-chalcogen reagents have been synthesized and characterized in order to probe their ability in this case.

The preparation of new bidentate ferrocenyl chalcogen reagents 1,1’-fc(C{O}OCH₂CH₂SH)₂ (fc = ferrocenyl) and 1,1’-fc(C{O}NHCH₂CH₂SH)₂ are presented. Furthermore, the preparation of silylated …

Uncovering New Bonding Motifs: The Synthesis Of Chalcogen And Phosphorus Complexes Supported By Nitrogen Based Ligands, Caleb D. Martin

Electronic Thesis and Dissertation Repository

The chemistry of the main group elements with nitrogen based ligands has been an area that has received little attention in comparison to transition metals. The preliminary investigations have focused on groups 13 and 14 revealing new bonding motifs and interesting reactivity. This has motivated us to synthesize group 15 and 16 derivatives in new bonding arrangements capable of activating small molecules.

In pursuit of isolating such species, the reactivity of sulfur dichloride and “S(OTf)2” with a series of diazabutadiene (DAB) ligands was explored. The substitution on the ligand was extremely influential on the outcome of the reaction. Alkyl groups …