The alarming growth in atmospheric CO2 has emerged as one of the prime concerns in the context of climate change. The power, petroleum, and construction sectors are the major contributors...

Synthesis and structural elucidation of a series of thiolate-bridged heterobimetallic MnCo complexes are described. Irradiation of [Mn 2 (CO) 10 ] in the presence of Li[BH 3 SPh] followed by room-temperature reaction with [Cp*CoCl] 2 (Cp* = η 5 -C 5 Me 5 ) afforded dithiolate-and hydride-bridged dinuclear heterobimetallic MnCo complex [{(Mn(CO) 3 }(μ-SPh) 2 (μ-H){CoCp*}] (1). The solid-state structure of 1 established that the two metal fragments, {Mn(CO) 3 } and {Cp*Co}, are linked by a Mn−Co bond. In addition to 1, the reaction also yielded half-sandwiched trithiolate-bridged dinuclear MnCo complex [{Mn(CO) 3 }(μ-SPh) 3 (CoCp*)] (2) and a dinuclear heterometal-coordinated diborane analogue [{Mn(CO) 3 }(μ-η 2 :η 2 -SBH 3 )-(μ-H)(CoCp*)] (3). To isolate the Se analogues of 1−3, a similar reaction was carried out in the presence of Li[BH 3 SePh] that led to the formation of complexes [{(Mn(CO) 3 }(μ-SePh) 2 (μ-H)(CoCp*)] ( 4), [{Mn(CO) 3 }(μ-SePh) 3 (CoCp*)] ( 5), and [{Mn(CO) 3 }(μ-η 2 :η 2 -SeBH 3 )(μ-H)(CoCp*)] (6). All of the complexes were characterized by employing multinuclear nuclear magnetic resonance and infrared spectroscopies as well as mass spectrometric techniques. Single-crystal X-ray diffraction analyses of complexes 1, 2, and 4 helped to establish the molecular formulations and structural integrity of these complexes. The bonding interactions present in these di-or trichalcogenate-bridged dinuclear heterobimetallic complexes were explicated computationally by density functional theory calculations that supported the {Mn−H−Co} and Mn−Co bonding interactions in 1 and 4. The inherent electronic properties of all of the complexes were demonstrated by ultraviolet−visible spectroscopy. Furthermore, the critical involvement of the bridging chalcogenato functionalities was probed via cyclic voltammetry and complementary spectroelectrochemical studies.