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Understanding the Early Stages of Nickel Sulfide Nanocluster Growth: Isolation of Ni 3 , Ni 4 , Ni 5 , and Ni 8 Intermediates
Author(s) -
Touchton Alexander J.,
Wu Guang,
Hayton Trevor W.
Publication year - 2021
Publication title -
small
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 3.785
H-Index - 236
eISSN - 1613-6829
pISSN - 1613-6810
DOI - 10.1002/smll.202003133
Subject(s) - nickel , sulfide , nickel sulfide , ligand (biochemistry) , biphenyl , reductive elimination , stoichiometry , oxidative addition , metal , chemistry , materials science , inorganic chemistry , organic chemistry , catalysis , biochemistry , receptor
Abstract Addition of sub‐stoichiometric quantities of PEt 3 and diphenyl disulfide to a solution of [Ni(1,5‐cod) 2 ] generates a mixture of [Ni 3 (SPh) 4 (PEt 3 ) 3 ] ( 1 ), unreacted [Ni(1,5‐cod) 2 ], and [(1,5‐cod)Ni(PEt 3 ) 2 ], according to 1 H and 31 P{ 1 H} NMR spectroscopic monitoring of the in situ reaction mixture. On standing, complex 1 converts into [Ni 4 (S)(Ph)(SPh) 3 (PEt 3 ) 3 ] ( 2 ), via formal addition of a “Ni(0)” equivalent, coupled with a CS oxidative addition step, which simultaneously generates the Ni‐bound phenyl ligand and the μ 3 ‐sulfide ligand. Upon gentle heating, complex 2 converts into a mixture of [Ni 5 (S) 2 (SPh) 2 (PEt 3 ) 5 ] ( 3 ) and [Ni 8 (S) 5 (PEt 3 ) 7 ] ( 4 ), via further addition of “Ni(0)” equivalents, in combination with a series of C–S oxidative addition and CC reductive elimination steps, which serve to convert thiophenolate ligands into sulfide ligands and biphenyl. The presence of 1 – 4 in the reaction mixture is confirmed by their independent syntheses and subsequent spectroscopic characterization. Overall, this work provides an unprecedented level of detail of the early stages of Ni nanocluster growth and highlights the fundamental reaction steps (i.e., metal atom addition, CS oxidative addition, and CC reductive elimination) that are required to grow an individual cluster.