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Addition of H2 across the cobalt–phosphorus bond of (PPP)CoPMe3 (3) is demonstrated, where PPP is a monoanionic diphosphine pincer ligand with a central N‐heterocyclic phosphido (NHP−) donor. The chlorophosphine CoII complex (PPClP)CoCl2 (2) can be generated through coordination of the chlorophosphine ligand (PPClP, 1) to CoCl2. Subsequent reduction of 2 with KC8 in the presence of PMe3 generates...
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