We investigate the electronic structure and bonding in 1 -4 using X-ray absorption and emission spectroscopy (XAS and XES) and (time-dependent) density functional theory (DFT and TD-DFT) calculations. Although X-ray spectroscopy studies of organometallic (including bimetallic) systems are common, insights into metal-metal bonding are often deduced only from metal-metal distance, with only a few reports of direct characterization of orbital interactions. In In a computational report, Zhang et al. calculated valence-to-core XES of dicobalt and diiron species, and identified a transition associated with metal-metal σ-bonding orbitals, suggesting the possibility of observing and quantifying these transitions experimentally. Here, we characterize Co-ligand and Co-Co interactions in 1 -4 using Co K-edge XAS and XES gaining detailed electronic structure insights and direct evidence for Co-Co σ-bonding. Using DFT, we construct the molecular orbital description to substantiate the experimentally-observed spectral features. We show that a multicentered bond forms, consisting of both direct Co-Co σ overlap and contributions from the silane ligands, which can be understood by considering ligand identity, coordination geometry, and d-electron count. We apply these insights to the compounds described by Deng and Nakajima to better describe and contextualize the nature of Co-Co and Co-ligand bonding in this class of compounds.