A cobalt deposition process, including: volatilizing a cobalt precursor selected from among CCTBA, CCTMSA, and CCBTMSA, to form a precursor vapor; and contacting the precursor vapor with a substrate under vapor deposition conditions effective for depositing on the substrate (i) high purity, low resistivity cobalt or (ii) cobalt that is annealable by thermal annealing to form high purity, low resistivity cobalt. Such cobalt deposition process can be used to manufacture product articles in which the deposited cobalt forms an electrode, capping layer, encapsulating layer, diffusion layer, or seed for electroplating of metal thereon, e.g., a semiconductor device, flat-panel display, or solar panel.