Studies Relevant to the Functional Model of Mo-Cu CODH: In Situ Reactions of Cu(I)-L Complexes with Mo(VI) and Synthesis of Stable Structurally Characterized Heterotetranuclear Mo^VI₂Cu^I₂ Complex

In this study, we report the synthesis, characterization, and reactions of Cu(I) complexes of the general form Cu(L)(LigH₂) (LigH₂ = xanthene-based heterodinucleating ligand (E)-3-(((5-(bis(pyridin-2-ylmethyl)amino)-2,7-di-tert-butyl-9,9-dimethyl-9H-xanthen-4-yl)imino)methyl)benzene-1,2-diol); L = PMe₃, PPh₃, CN(2,6-Me₂C₆H₃)). New complexes [Cu(PMe₃)(LigH₂)] and [CuCN(2,6-Me₂C₆H₃)(LigH₂)] were synthesized by treating [Cu(LigH₂)](PF₆) with trimethylphosphine and 2,6-dimethylphenyl isocyanide, respectively. These complexes were characterized by multinuclear NMR spectroscopy, IR spectroscopy, high-resolution mass spectrometry (HRMS), and X-ray crystallography. In contrast, attempted reactions of [Cu(LigH₂)](PF₆) with cyanide or styrene failed to produce isolable crystalline products. Next, the reactivity of these and previously synthesized Cu(I) phosphine and isocyanide complexes with molybdate was interrogated. IR (for isocyanide) and ³¹P NMR (for PPh₃/PMe₃) spectroscopy demonstrates the lack of oxidation reactivity. We also describe herein the first example of a structurally characterized multinuclear complex combining both Mo(VI) and Cu(I) metal ions within the same system. The heterobimetallic tetranuclear complex [Cu₂Mo₂O₄(μ₂-O)(Lig)₂]·HOSiPh₃ was obtained by the reaction of the silylated Mo(VI) precursor (Et₄N)(MoO₃(OSiPh₃)) with LigH₂, followed by the addition of [Cu(NCMe)₄](PF₆). This complex was characterized by NMR spectroscopy, high-resolution mass spectrometry, and X-ray crystallography.