Issue 47, 2022

N-heterocyclic carbene and cyclic (alkyl)(amino)carbene complexes of molybdenum(iv) and tungsten(iv)

Abstract

The synthesis and characterization of N-heterocyclic carbene (NHC) and cyclic (alkyl)(amino)carbene (cAAC) complexes of molybdenum(IV) and tungsten(IV) chloride is reported. Reaction of two equivalents of the NHCs IMes (1,3-bis(2,4,6-trimethylphenyl)imidazolin-2-ylidene), IDipp (1,3-bis(2,6-diisopropylphenyl)imidazolin-2-ylidene) and IiPrMe (1,3-diisopropyl-4,5-dimethylimidazolin-2-ylidene) with [MCl4(SEt)2] (M = Mo, W) in toluene afforded the bis-NHC complexes [MCl4(NHC)2] (M = Mo: NHC = IMes 1, NHC = IMes 2; M = W: NHC = IMes 3, NHC = IDipp 4, NHC = IiPrMe5). Mono-carbene complexes [MCl4(NHC)(SEt2)] 6–9 (M = Mo: NHC = IMes 6, NHC = IMes 7; M = W: NHC = IMes 8, NHC = IDipp 9) are available via ligand dismutation of 1–4 with [MCl4(SEt)2]. Complexes 1–9 were characterized by using elemental analysis, IR- and multinuclear NMR spectroscopy and X-ray diffraction for 1–8. The reactivity of the mono-NHC complexes 6–9 towards the cyclic (alkyl)(amino)carbene cAACMe as well as the two electron donor ligands trimethylphosphine, triphenylphosphine, pyridine (py) and N,N-dimethylpyridin-4-amine (DMAP) was studied, which led to the synthesis of the mixed substituted complexes [MCl4(NHC)(cAACMe)] (M = Mo: NHC = IMes 10, NHC = IDipp 11; M = W: NHC = IMes 12, NHC = IDipp 13), [MCl4(NHC)(PR3)] (M = W: NHC = IMes, R = Me 14, NHC = IMes, R = Ph 15, NHC = IDipp, R = Me 16, NHC = IDipp, R = Ph 17), [MCl4(NHC)(py)] (M = Mo: NHC = IMes 18, NHC = IDipp 20; M = W: NHC = IMes 22, NHC = IDipp 24) and [MCl4(NHC)(DMAP)] (M = Mo: NHC = IMes 19, NHC = IDipp 21; M = W: NHC = IMes 23, NHC = IDipp 25).

Graphical abstract: N-heterocyclic carbene and cyclic (alkyl)(amino)carbene complexes of molybdenum(iv) and tungsten(iv)

Supplementary files

Article information

Article type
Paper
Submitted
20 Oct 2022
Accepted
12 Nov 2022
First published
14 Nov 2022

Dalton Trans., 2022,51, 18337-18352

N-heterocyclic carbene and cyclic (alkyl)(amino)carbene complexes of molybdenum(IV) and tungsten(IV)

C. Luz, E. Glok, G. Horrer and U. Radius, Dalton Trans., 2022, 51, 18337 DOI: 10.1039/D2DT03409C

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