In this mini-review, we summarize the solution syntheses of N,N-dimethylformamide (DMF)-protected metal nanoparticles (NPs) and nanoclusters (NCs) and their use in catalytic reactions. Representative examples are given of external-stabilizer/protectant-free metal NP and NC syntheses by reduction with DMF. In this method, DMF has three roles, i.e., a solvent, reductant, and protectant. Recent applications of DMF-stabilized metal NPs are summarized. These applications have enabled a versatile organic transformation such as cross-coupling reactions, hydrosilylation, and methylation to be achieved. These reactions proceed under low catalyst loadings and ligandless conditions.
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