Combining [Mo^VIO₃] and [M⁰(CO)₃] (M = Mo, Cr) Fragments within the Same Complex: Synthesis and Reactivity of the Single Oxo-Bridged Heterobimetallics Supported by Xanthene-Based Heterodinucleating Ligands

Abstract

A functional model of Mo−Cu carbon monoxide dehydrogenase (CODH) enzyme requires the presence of an oxidant (metal-oxo) and a metal-bound carbonyl in close proximity. In this work, we report the synthesis, characterization, and reactivity of a heterobimetallic complex combining Mo(VI) trioxo with Mo(0) tricarbonyl. The formation of the heterobimetallic complex is facilitated by the xanthene-bridged heterodinucleating ligand containing a hard catecholate chelate and a soft iminopyridine chelate. A catechol-coordinated square-pyramidal [Mo VI O 3 ] fragment interacts directly with the iminopyridine-bound [Mo 0 (CO) 3 ] fragment via a single (oxo) bridge, with the overall disposition being related to the proposed first step in the CODH mechanism, where square-pyramidal [Mo VI O 2 S] interacts with the [Cu−CO] via a single sulfido bridge. Our attempt to obtain a sulfido-bridged analogue (using [MoO 3 S] 2− precursor) led to a mixture of products possibly containing different (oxo and sulfido) bridges. Despite a direct interaction between Mo(VI) and Mo(0) segments, no internal redox is observed, with the high lying occupied MOs being mostly d-π orbitals at Mo 0 (CO) 3 and the low lying unoccupied MOs being d-π orbitals at Mo VI O 3 . Due to the overall rigid structure, the heterobimetallic complex was found to be stable up to 100 °C in DMF-d 7 (based on 1 H NMR). The decomposition of the complex above this temperature does not produce CO 2 (based on gas chromatography), dissociating stable Mo(CO) 3 (DMF) 3 instead (based on IR). We also synthesized and studied the reactivity of the Mo(VI)/Cr(0) analogue. While this complex demonstrated more facile decomposition, no CO 2 production was observed. Density functional theory calculations suggest that the formation of [CO 2 ] 2− and its subsequent reductive elimination is endergonic in the present system, likely due to the stability of fac-Mo 0 (CO) 3 and the relative nucleophilic character of the carbonyl carbon engendered by back donation from Mo(0). The calculations also indicate that the replacement of one oxo by sulfido (both terminal and bridging), replacement of catechol with dithiolene, and replacement of Mo(0) with Cr(0) does not affect significantly the energetics of the process, likely requiring the use a less stable and less π-basic CO anchor.