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Creators/Authors contains: "Mendelsohn, Lauren N"

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  1. Abstract Intermediates relevant to cobalt‐catalyzed alkene hydroformylation have been isolated and evaluated in fundamental organometallic transformations relevant to aldehyde formation. The 18‐electron (R,R)‐(iPrDuPhos)Co(CO)2H has been structurally characterized, and it promotes exclusive hydrogenation of styrene in the presence of 50 bar of H2/CO gas (1:1) at 100 °C. Deuterium‐labeling studies established reversible 2,1‐insertion of styrene into the Co−D bond of (R,R)‐(iPrDuPhos)Co(CO)2D. Whereas rapid β‐hydrogen elimination from cobalt alkyls occurred under an N2atmosphere, alkylation of (R,R)‐(iPrDuPhos)Co(CO)2Cl in the presence of CO enabled the interception of (R,R)‐(iPrDuPhos)Co(CO)2C(O)CH2CH2Ph, which upon hydrogenolysis under 4 atm H2produced the corresponding aldehyde and cobalt hydride, demonstrating the feasibility of elementary steps in hydroformylation. Both the hydride and chloride derivatives, (X=H, Cl), underwent exchange with free13CO. Under reduced pressure, (R,R)‐(iPrDuPhos)Co(CO)2Cl underwent CO dissociation to form (R,R)‐(iPrDuPhos)Co(CO)Cl. 
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