The reactions of heavier group 14 element alkyne analogues (EAriPr4)2 (E = Ge, Sn; AriPr4 = C6H3-2,6-(C6H3-2,6-iPr2)2) with the group 6 transition-metal carbonyls M(CO)6 (M = Cr, Mo, W) under UV irradiation resulted in the cleavage of the E–E triple bond and the formation of the complexes {AriPr4EM(CO)4}2 (1–6), which were characterized by single crystal X-ray diffraction as well as by IR and multinuclear NMR spectroscopy. Single-crystal X-ray structural analyses of 1–6 showed that the complexes have a nearly planar rhomboid M2E2 core with three-coordinate group 14 atoms. The coordination geometry at the group 6 metals is distorted octahedral formed by four carbonyl groups as well as two bridging EAriPr4 units. IR spectroscopic data suggest that the EAriPr4 units are not very efficient π-acceptors, but the investigation of E–M metal–metal interactions in 1–6 with computational methods revealed the importance of both σ- and π-type contributions to bonding. The mechanism for the insertion of transition-metal carbonyls into E–E bonds in (EAriPr4)2 was also probed computationally.