Scheme 2.

Reaction scheme suggested for in situ formation of nickel nanocrystallite: Pre-formed Ni (II) complex (1) offers the nucleophilic attack of N atom of the silylamino group on the center Ni(II) cation to replace Cl (2). Subsequently, Ni-N bond formation proceeds accompanied by the attack of the released chloride anion (Cl^–) on other electrophiles, such as Si center of PHPS moieties (3). The resulting species with a Ni-N bond (4) decompose to give nickel nitride species (a possible one is Ni₃N) (5). Subsequent decomposition of (5) is facilitated by an in situ-formed H₂ leads to the formation of Ni (0) (6), followed by the nucleation and crystallization of Ni (7) at 200 to 300 °C.