Synthesis and characterization of heptacoordinated molybdenum(II) complexes supported with 2,6-bis(pyrazol-3-yl)pyridine (bpp) ligands.

Functional pincer ligands that engage in metal-ligand cooperativity and/or are capable of redox non-innocence have found a great deal of success in catalysis. These two properties may be found in metal complexes of the 2,6-bis(pyrazol-3-yl)pyridine (bpp) ligands. With this goal in mind, we have attempted the coordination of 2,6-bis(5-trifluoromethylpyrazol-3-yl)pyridine (LCF3) and its Bu analogue 2,6-bis(5--butylpyrazol-3-yl)pyridine (LtBu) to Mo(0) by reactions with mixed phosphine/carbonyl complexes [Mo(CO)(MeCN)(PMePh)] 1-3 (1 ≤ ≤ 3). These afforded mixtures of several Mo compounds among which low yields of heptacoordinated Mo(II) complexes [Mo(CO)(bpp)(PMePh)] 4a-c (LCF3-supported) and 5a-c (LtBu-supported) bearing a doubly deprotonated bpp ligand were systematically produced. More selective syntheses of 4a-c and 5a-c were achieved by repeating these experiments in the presence of an oxidant (AgOAc or AgO), with moderate to good yields. 4a-c and 5a-c were characterized by means of NMR, IR and UV-Vis spectroscopies, sc-XRD and cyclic and square-wave voltammetries for 4a, 4b and 5b. The deprotonated LtBu ligand in 5a-c is re-protonated with 2 equiv. of HOTf to afford the dicationic [Mo(CO)(LtBu)(PMePh)][OTf] complexes 6a-c. Acidic treatment of 4a-c led to the decomposition of the complexes.