We have recently reported the preparation and structural characteristics of group 15 M[N(SiMe3)2]3 complexes (Inorg. Chem. 2014, 53, 9703). They are characterized by extremely crowded coordination environments provided by the bulky bis(trimethylsilyl)amido ligands (e.g., the effective cone angle of the phosphorus compound (pictured) is 241°). We have begun examining the consequences of such steric congestion on the ability of the compounds to serve as ligands to metals and as reagents for synthetic chemistry. These include the ability of P[N(SiMe3)2]3 to act as a reducing and capping agent in nanoparticle synthesis in solution and solid state reactions. Investigations into the use of the complexes as participants in frustrated Lewis pair (FLP) chemistry have also been conducted. Preparation of synthetic derivatives of the complexes, such as E = P[N(SiMe3)2]3 (E = O, S, Se), will also be discussed.

Steric bulk as both inhibitor and promoter of reactivity: the case of group 15 M[N(SiMe3)2]3 complexes

249th National Meeting (2015)

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