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This is an open access article published by MDPI and distributed under the  Creative Commons Attribution License (CC BY 4.0) which permits unrestricted use, distribution, and reproduction in any medium, provided the original work is properly cited.Reaction of the bulky bi-phenols 2,2′-RCH[4,6-(t-Bu)2C6H2OH]2 (R = Me L1MeH2, Ph L1PhH2) with the bis(imido) molybdenum(VI) tert-butoxides [Mo(NR1)(NR2)(Ot-Bu)2] (R1 = R2 = 2,6-C6H3-i-Pr2; R1 = t-Bu, R2 = C6F5) afforded, following the successive removal of tert-butanol, the complexes [Mo(NC6H3i-Pr2-2,6)2L1Me] (1), [Mo(NC6H3i-Pr2-2,6)2L1Ph] (2) and [Mo(Nt-Bu)(μ-NC6F5)(L1Me)]2 (3). Similar use of the tri-phenol 2,6-bis(3,5-di-tert -butyl-2-hydroxybenzyl)-4-methylphenol (L2H3) with [Mo(NC6H3i-Pr2-2,6)2(Ot-Bu)2] afforded the oxo-bridged product [Mo(NC6H3i-Pr2-2,6)(NCMe)(μ-O)L2H]2 (4), whilst use of the tetra-phenols α,α,α′,α′-tetrakis(3,5-di-tert-butyl-2-hydroxyphenyl)-p- or -m-xylene L3pH4/L3mH4 led to {[Mo(NC6H3i-Pr2-2,6)2]2(μ-L3p)} (5) or {[Mo(NC6H3i-Pr2-2,6)2]2(μ-L3m)} (6), respectively. Similar use of [Mo(NC6F5)2(Ot-Bu)2] with L3pH4 afforded, after work-up, the complex {[Mo(NC6F5)(Ot-Bu)2]2(μ-L3p)}·6MeCN (7·6MeCN). Molecular structures of 1, 2·CH2Cl2, 3, 4·6MeCN, 6·2C6H14, and 7·6MeCN are reported and these complexes have been screened for their ability to ring open polymerize (ROP) ε-caprolactone; for comparative studies the precursor complex [Mo(NC6H3i-Pr2-2,6)2Cl2(DME)] (DME = 1,2-dimethoxyethane) has also been screened. Results revealed that good activity is only achievable at temperatures of ≥100 °C over periods of 1 h or more. Polymer polydispersities were narrow, but observed molecular weights (Mn) were much lower than calculated values

Molybdenum (VI) Imido Complexes Derived from Chelating Phenols: Synthesis, Characterization and ɛ-Caprolactone ROP Capability