Abstract
The reaction of Na2MoO4 with 2,2'-oxydianiline (2-aminophenylether), (2-NH2C6H4)2O, LH4, in DME (DME = 1,2-dimethoxyethane) in the presence of Et3N and Me3SiCl afforded either the bis(imido) molybdenum(vi) complex {Mo(L)Cl2(DME)} (), where L = (2-NC6H4)2O, or the molybdenum(v) salt [Mo(L')Cl4][Et3NH] (), where L' = [(2-NH2C6H4)(2-NC6H4)O], depending on the work-up method employed. The same diamine reacted with in situ [Mo(NtBu)2Cl2(DME)] afforded a tetra-nuclear complex [Mo4Cl3(NtBu)3(OSiMe3)(μ4-O)(L)2(L')2]·2MeCN (·2MeCN). The crystal structures of , and ·2MeCN have been determined. The structure of the bis(imido) complex contains two unique molecules paired up via weak π-stacking, whereas the structure of contains a chelating amine/imido ligand, and is made up of discrete units of two cations and two anions which are interacting via H-bonding. The tetra-nuclear structure contains four different types of distorted octahedral molybdenum centre, and a bent Me3SiO group thought to originate from the precursor synthesis. Complexes have been screened for their ability to ring open polymerize (ROP) ε-caprolactone. For and (not ), conversion rates were good (>90%) at high temperatures (100 °C) over 6-24 h, and the polymerization proceeded in a living manner.
Highlights
45 complex 2 bearing a chelating amine/imide ligand in the anion, Entry into molybdenum(VI) organoimido [Mo=NR] chemistry, 20 which has proved pivotal in designing new ring opening metathesis polymerization (ROMP) catalysts over the years, [1] is convenient via the one-pot ‘sodium molybdate’ route, [2] or when basicity permits, the ‘tert-butylimido exchange’ route. [3] Such methods have allowed for the introduction of a range of 25 organoimido groups with varying electronic and steric properties, which can be used to affect/control the polymerization processes
Mononuclear Mo(VI) bis(imido) complex 1 or a Mo(V) salt 45 complex 2 bearing a chelating amine/imide ligand in the anion, Entry into molybdenum(VI) organoimido [Mo=NR] chemistry, 20 which has proved pivotal in designing new ring opening metathesis polymerization (ROMP) catalysts over the years, [1] is convenient via the one-pot ‘sodium molybdate’ route, [2] or when basicity permits, the ‘tert-butylimido exchange’ route
A search of the Cambridge Crystallographic database (CSD) revealed 62 hits for motifs derived from (2-NH2C6H4)2O binding to any metal; the majority of these examples contained larger ligands incorporating the backbone of the dianiline
Summary
45 complex 2 bearing a chelating amine/imide ligand in the anion, Entry into molybdenum(VI) organoimido [Mo=NR] chemistry, 20 which has proved pivotal in designing new ring opening metathesis polymerization (ROMP) catalysts over the years, [1] is convenient via the one-pot ‘sodium molybdate’ route, [2] or when basicity permits, the ‘tert-butylimido exchange’ route. [3] Such methods have allowed for the introduction of a range of 25 organoimido groups with varying electronic and steric properties, which can be used to affect/control the polymerization processes. 101.21(11) o, which is similar to the bite angle observed for the 8membered ring formed in the chelating bis(imide) complex {Mo[(2-NC6H4)2CH2]Cl2(DME)} [100.8(5) o] derived from I (n = 1).
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