ja0438821_si_003.cif (14.17 kB)
Steric and Electronic Properties of N-Heterocyclic Carbenes (NHC): A Detailed Study on Their Interaction with Ni(CO)4
dataset
posted on 2005-03-02, 00:00 authored by Reto Dorta, Edwin D. Stevens, Natalie M. Scott, Chiara Costabile, Luigi Cavallo, Carl D. Hoff, Steven P. NolanN-heterocyclic carbene ligands IMes (1), SIMes (2), IPr (3), SIPr (4), and ICy (5) react with
Ni(CO)4 to give the saturated tricarbonyl complexes Ni(CO)3(IMes) (8), Ni(CO)3(SIMes) (9), Ni(CO)3(IPr)
(10), Ni(CO)3(SIPr) (11), and Ni(CO)3(ICy) (12), respectively. The electronic properties of these complexes
have been compared to their phosphine analogues of general formula Ni(CO)3(PR3) by recording their νCO
stretching frequencies. While all of these NHCs are better donors than tertiary phosphines, the differences
in donor properties between ligands 1−5 are surprisingly small. Novel, unsaturated Ni(CO)2(IAd) (13) and
Ni(CO)2(ItBu) (14) compounds are obtained from the reaction of Ni(CO)4 with IAd (6) and ItBu (7). Complexes
13 and 14 are highly active toward substitution of the NHC as well as the carbonyl ligands. This has allowed
the determination of Ni−C(NHC) bond dissociation energies and the synthesis of various unsaturated Ni(0) and Ni(II) complexes. Computational studies on compounds 8−14 are in line with the experimental
findings and show that IAd (6) and ItBu (7) are more bulky than IMes (1), SIMes (2), IPr (3), SIPr (4), and
ICy (5). Furthermore, a method based on %Vbur values has been developed for the direct comparison of
steric requirements of NHCs and tertiary phosphines. Complexes 8−14, as well as NiCl(C3H5)(ItBu) (16)
and NiBr(C3H5)(ItBu) (17), have been characterized by X-ray crystallography.
