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Abstract Addition of sub‐stoichiometric quantities of PEt3and diphenyl disulfide to a solution of [Ni(1,5‐cod)2] generates a mixture of [Ni3(SPh)4(PEt3)3] (1), unreacted [Ni(1,5‐cod)2], and [(1,5‐cod)Ni(PEt3)2], according to1H and31P{1H} NMR spectroscopic monitoring of the in situ reaction mixture. On standing, complex1converts into [Ni4(S)(Ph)(SPh)3(PEt3)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 μ3‐sulfide ligand. Upon gentle heating, complex2converts into a mixture of [Ni5(S)2(SPh)2(PEt3)5] (3) and [Ni8(S)5(PEt3)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 of1–4in 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.
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Germanium(II) Dithiolene Complexes
Abstract The 1 : 2 reaction of the imidazole‐based dithiolate (2) with GeCl2 • dioxane in THF/TMEDA gives3, a TMEDA‐complexed dithiolene‐based germylene. Compound3is converted to monothiolate‐complexed (5) and N‐heterocyclic carbene‐complexed (7) germanium(II) dithiolene complexes via Lewis base ligand exchange. A bis‐dithiolene‐based germylene (8), involving a 3c–4e S‐Ge‐S bond, has also been synthesized through controlled hydrolysis of7. The bonding nature of3,5, and8was investigated by both experimental and theoretical methods.
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- Award ID(s):
- 2153978
- PAR ID:
- 10468822
- Publisher / Repository:
- Wiley Blackwell (John Wiley & Sons)
- Date Published:
- Journal Name:
- Chemistry – A European Journal
- Volume:
- 29
- Issue:
- 65
- ISSN:
- 0947-6539
- Format(s):
- Medium: X
- Sponsoring Org:
- National Science Foundation
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