TY - JOUR
T1 - Characterization of Rh(I) complexes bearing N-2-nitrobenzenesulfonyl substituted, N-heterocyclic carbenes
AU - Sato, Tetsuo
AU - Yoshioka, Daisuke
AU - Hirose, Yoichi
AU - Oi, Shuichi
N1 - Funding Information:
This work was supported in part by a Grant-in-Aid for Scientific Research on Innovative Areas “Molecular Activation Directed toward Straightforward Synthesis” from MEXT , Japan and by a commissioned project conducted by New Energy and Industrial Technology Development Organization (NEDO).
PY - 2014/3/1
Y1 - 2014/3/1
N2 - Synthesis and structural characterization of novel Rh(I) complexes bearing 1,2,4-triazol-3-ylidene or imidazol-2-ylidene substituted with an N-2-nitrobenzenesulfonyl (N-nosyl) group are described. The complexes were characterized by infrared (IR), NMR, and single-crystal X-ray diffraction analyses. The Tolman electronic parameter (TEP) values of both of the 1,2,4-triazol-3-ylidene (2064 cm-1) and imidazol-2-ylidene (2059 cm-1), as determined from the average carbonyl (CO) stretching frequencies for the corresponding RhCl(NHC)(CO)2 (NHC = N-heterocyclic carbene) complexes, were higher than that of RhCl(IMes)(CO) 2 (IMes = 1,3-bis(2,4,6-trimethylphenyl)imidazol-2-ylidene) (2050 cm-1). As the TEP values of the NHCs increased, the 13C NMR signal of the carbenic carbon in the corresponding RhCl(NHC)(cod) (cod = 1,5-cyclooctadiene) and RhCl(NHC)(CO)2 complexes shifted downfield. Moreover, the crystallographic analysis of the RhCl(NHC)(cod) complexes revealed that one of the SO bonds in the sulfonyl group could be conjugated with the NHC frameworks, while the remaining SO bond conjugated with the 2-nitrophenyl groups of the N-nosyl substituent.
AB - Synthesis and structural characterization of novel Rh(I) complexes bearing 1,2,4-triazol-3-ylidene or imidazol-2-ylidene substituted with an N-2-nitrobenzenesulfonyl (N-nosyl) group are described. The complexes were characterized by infrared (IR), NMR, and single-crystal X-ray diffraction analyses. The Tolman electronic parameter (TEP) values of both of the 1,2,4-triazol-3-ylidene (2064 cm-1) and imidazol-2-ylidene (2059 cm-1), as determined from the average carbonyl (CO) stretching frequencies for the corresponding RhCl(NHC)(CO)2 (NHC = N-heterocyclic carbene) complexes, were higher than that of RhCl(IMes)(CO) 2 (IMes = 1,3-bis(2,4,6-trimethylphenyl)imidazol-2-ylidene) (2050 cm-1). As the TEP values of the NHCs increased, the 13C NMR signal of the carbenic carbon in the corresponding RhCl(NHC)(cod) (cod = 1,5-cyclooctadiene) and RhCl(NHC)(CO)2 complexes shifted downfield. Moreover, the crystallographic analysis of the RhCl(NHC)(cod) complexes revealed that one of the SO bonds in the sulfonyl group could be conjugated with the NHC frameworks, while the remaining SO bond conjugated with the 2-nitrophenyl groups of the N-nosyl substituent.
KW - 2-Nitrobenzenesulfonyl group
KW - Electronic property
KW - N-Heterocyclic carbene
KW - Rhodium complex
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U2 - 10.1016/j.jorganchem.2013.12.024
DO - 10.1016/j.jorganchem.2013.12.024
M3 - Article
AN - SCOPUS:84891683981
SN - 0022-328X
VL - 753
SP - 20
EP - 26
JO - Journal of Organometallic Chemistry
JF - Journal of Organometallic Chemistry
ER -