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Issue 9, 2012
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Synthesis of N-heterocyclic carbene rhenium(I) carbonyl complexes

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Reaction of aminophosphinimine [RHN(CH2)2N[double bond, length as m-dash]PPh3] (R = H, Et) with Re2(CO)10 provided the NH-functionalized carbene rhenium complex [Re2(CNHCH2CH2NR)(CO)9] (3a, R = H, 3b, R = Et). Treatment of 3 with Br2 provided the mono nuclear [Re(CNHCH2CH2NR)(CO)4Br] (1, R = H, 2, R = Et). However, NH-functionalized carbene complexes 13 did not undergo N-alkylation with alkyl halides to yield the N-substituted NHC complexes. The direct ligand substitution of [Re(CO)5Br] with a carbene donor was employed to prepare [Re(IMes2)(CO)4Br] (6a, IMes2 = 1,3-di-mesitylimidazol-2-ylidene; 6b, IMes2 = 1,3-dimesityl-4,5-dihydroimidazol-2-ylidene). Analyses of spectroscopic and crystal data of 6a and 6b show similar corresponding data among these complexes, suggesting the saturated and unsaturated NHCs have similar bonding with ReI metal centers. Reduction of 6a and 6b with LiEt3BH yielded the corresponding hydrido complexes 7ab [ReH(CO)4(IMes2)], but not 1 and 2. Ligand substitution of 1, 6a and 6b toward 2,2′-bipyridine (bipy) was investigated. Crystal structures of 1, 3ab, 6ab and 7b were determined for characterization and comparison.

Graphical abstract: Synthesis of N-heterocyclic carbene rhenium(i) carbonyl complexes

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The article was received on 19 Oct 2011, accepted on 23 Nov 2011 and first published on 17 Jan 2012

Article type: Paper
DOI: 10.1039/C2DT11974A
Citation: Dalton Trans., 2012,41, 2747-2754
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    Synthesis of N-heterocyclic carbene rhenium(I) carbonyl complexes

    C. Chen, Y. Liu, S. Peng, J. Chen and S. Liu, Dalton Trans., 2012, 41, 2747
    DOI: 10.1039/C2DT11974A

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