메뉴 건너뛰기




Volumn 49, Issue 39, 2010, Pages 6940-6952

The measure of all rings - N-Heterocyclic carbenes

Author keywords

Electronic structure; Homogeneous catalysis; Ligand design; N heterocyclic carbenes; Steric hinderance

Indexed keywords

AS-LIGANDS; BOND STRENGTH; CHARACTERISTIC PROPERTIES; HOMOGENEOUS CATALYSIS; LIGAND DESIGN; METAL CATALYSIS; N-HETEROCYCLIC CARBENES; ORGANOCATALYSTS; ORGANOMETALLIC CHEMISTRY; PHYSICO-CHEMICAL DATA; RESEARCH FIELDS; STERIC HINDERANCES; STERICS;

EID: 77956894584     PISSN: 14337851     EISSN: 15213773     Source Type: Journal    
DOI: 10.1002/anie.201001865     Document Type: Review
Times cited : (1094)

References (217)
  • 4
    • 0001175757 scopus 로고
    • a) Thus, the question "Stable Carbenes - Illusion or Reality ?" (M. Regitz, Angew. Chem. 1991, 103, 691;
    • (1991) Angew. Chem. , vol.103 , pp. 691
    • Regitz, M.1
  • 5
    • 33750155559 scopus 로고
    • was unequivocally answered
    • Angew. Chem. Int. Ed. Engl. 1991, 30, 674.) was unequivocally answered
    • (1991) Angew. Chem. Int. Ed. Engl. , vol.30 , pp. 674
  • 10
    • 77956912347 scopus 로고    scopus 로고
    • f) In some cases, the NHCs mentioned in this review were only reported as ligands in metal-NHC complexes, and not as free NHCs. Thus, throughout this review the depiction of the NHC does not necessarily mean that the free NHC was either observed or isolated.
    • f) In some cases, the NHCs mentioned in this review were only reported as ligands in metal-NHC complexes, and not as free NHCs. Thus, throughout this review the depiction of the NHC does not necessarily mean that the free NHC was either observed or isolated.
  • 22
    • 3142640259 scopus 로고
    • For the mechanistic elucidation of the mode of action of coenzyme thiamine, see: R. Breslow, J. Am. Chem. Soc. 1958, 80, 3719.
    • (1958) J. Am. Chem. Soc. , vol.80 , pp. 3719
    • Breslow, R.1
  • 34
    • 36849065859 scopus 로고    scopus 로고
    • Ed. S. P. Nolan, Wiley-vCH Weinheim Germany
    • d) N-Heterocyclic Carbenes in Synthesis (Ed. : S. P. Nolan), Wiley-VCH, Weinheim, Germany, 2006
    • (2006) N-heterocyclic Carbenes in Synthesis
  • 98
    • 77956940967 scopus 로고    scopus 로고
    • b) For various methods to rank phophines according to their net donating ability, as well as scales based on metalcarbonyl complexes and their calibration in respect with TEP, see: O. Kiihl, Coord. Chem. Rev. 2005, 249, 693.
    • (2005) Coord. Chem. Rev. , vol.249 , pp. 693
    • Kiihl, O.1
  • 104
    • 77950266144 scopus 로고    scopus 로고
    • For seminal cyclic voltammetric measurement of NHC containing metal complexes, see: a) V. Sashuk, L. H. Peeck, H. Plenio, Chem. Eur. J. 2010, 16, 3983
    • (2010) Chem. Eur. J. , vol.16 , pp. 3983
    • Sashuk, V.1    Peeck, L.H.2    Plenio, H.3
  • 113
    • 77956899621 scopus 로고    scopus 로고
    • This represents the equation obtained and used by Nolan et al. in ref. [25k], however, without rounding it out.
    • This represents the equation obtained and used by Nolan et al. in ref. [25k], however, without rounding it out.
  • 115
    • 77956923681 scopus 로고    scopus 로고
    • coav/Ir [cm-1]-139.7 [cm-1]; R2 = 0.97.
    • ṽcoav/Ir [cm-1] = 0. 8695ṽcoav/Ir [cm-1] + 250.7 [cm-1]; ṽcoav/Ir [cm"1] = 1.116ṽcoav/Ir [cm-1]-139.7 [cm-1]; R2 = 0.97.
  • 116
    • 73949104823 scopus 로고    scopus 로고
    • Notbly, a correlation between the electrochemical potential E0 and the TEP is generally possible but more data have to be collected. T. Vorfalt, S. Leuthäußer, H. Plenio, Angew. Chem. 2009, 121, 5293
    • (2009) Angew. Chem. , vol.121 , pp. 5293
    • Vorfalt, T.1    Leuthäußer, S.2    Plenio, H.3
  • 117
    • 70349921088 scopus 로고    scopus 로고
    • see also ref. [35].
    • Angew. Chem. Int. Ed. 2009, 48, 5191 see also ref. [35].
    • (2009) Angew. Chem. Int. Ed. , vol.48 , pp. 5191
  • 119
    • 77956902206 scopus 로고    scopus 로고
    • 2] complex are as follows (in cm-1): 13a: ṽsym = 2073, ṽsym = 2004; 13b: ṽsym = 2068, ṽsym = 1989; 13c: ṽsym = 2072, ṽsym = 1989. The IR spectra were determined from a film.
    • b) carbonyl stretching frequencies of the corresponding [(NHC)RhCl(CO)2] complex are as follows (in cm-1): 13a: ṽsym = 2073, ṽsym = 2004; 13b: ṽsym = 2068, ṽsym = 1989; 13c: ṽsym = 2072, ṽsym = 1989. The IR spectra were determined from a film.
  • 130
    • 51249113510 scopus 로고    scopus 로고
    • See also
    • Angew. Chem. Int. Ed. 2008, 47, 5411. See also
    • (2008) Angew. Chem. Int. Ed. , vol.47 , pp. 5411
  • 133
    • 47949083075 scopus 로고    scopus 로고
    • for a short review on carbodicarbenes
    • Angew. Chem. Int. Ed. 2008, 47, 3210; for a short review on carbodicarbenes
    • (2008) Angew. Chem. Int. Ed. , vol.47 , pp. 3210
  • 139
    • 77956910075 scopus 로고    scopus 로고
    • b) The carbonyl stretching frequencies of the corresponding [(NHC)IrCl(CO)2] complex are as follows (in cm-1): 15a: ṽcosym = 2064, ṽcosym = 1978; 15b: ṽcosym = 2063, ṽcosym = 1977; 15c: ṽcosym = 2063, ṽcosym = 1976; 15d: ṽcosym = 2062, ṽcosym = 1976. The IR spectra were taken in CH2Cl2.
    • b) The carbonyl stretching frequencies of the corresponding [(NHC)IrCl(CO)2] complex are as follows (in cm-1): 15a: ṽcosym = 2064, ṽcosym = 1978; 15b: ṽcosym = 2063, ṽcosym = 1977; 15c: ṽcosym = 2063, ṽcosym = 1976; 15d: ṽcosym = 2062, ṽcosym = 1976. The IR spectra were taken in CH2Cl2.
  • 141
    • 77956903619 scopus 로고    scopus 로고
    • b) The carbonyl stretching frequencies of the corresponding [(NHC)RhCl(CO)2] complex are as follows (in cm-1): 16a: ṽcosym = 2099, ṽcosym = 2017; 16b: ṽcosym = 2091, ṽcosym = 2010; 16c: ṽcosym = 2087, ṽcosym = 2004. The IR spectra were taken in [D]chloroform.
    • b) The carbonyl stretching frequencies of the corresponding [(NHC)RhCl(CO)2] complex are as follows (in cm-1): 16a: ṽcosym = 2099, ṽcosym = 2017; 16b: ṽcosym = 2091, ṽcosym = 2010; 16c: ṽcosym = 2087, ṽcosym = 2004. The IR spectra were taken in [D]chloroform.
  • 143
    • 77956909455 scopus 로고    scopus 로고
    • cosym = 1996. The IR spectra were recorded using KBr pellets.
    • b) The carbonyl stretching frequencies of the corresponding [(NHC)RhCl(CO)2] complex are as follows (in cm-1): 17a: ṽcosym = 2088, ṽcosym = 2002; 17b: ṽcosym = 2084, ṽcosym = 2003; 17c: ṽcosym = 2074, ṽcosym = 1996. The IR spectra were recorded using KBr pellets.
  • 159
    • 77956922841 scopus 로고    scopus 로고
    • 2] tends to indicate that 30 is a significantly better donor than IMes or SIMes.
    • Instead of determining the TEP of 30, a series of [CpFe- (NHC)(CO)2]+I" complexes was synthesized and the carbonyl stretching frequencies measured [ṽCO bands for IMes (ṽn = 2050 and 2006 cm-1) and SIMes (ṽ = 2049 and 2005 cm-1)]. The observation of ṽCO bands at 2038 and 1993 cm-1 for the zwitterionic equivalent [CpFe(30)(CO)2] tends to indicate that 30 is a significantly better donor than IMes or SIMes.
  • 161
    • 77956900174 scopus 로고    scopus 로고
    • For the synthesis of 32a und [(32a)RhCl(cod)]
    • For the synthesis of 32a und [(32a)RhCl(cod)]
  • 166
    • 61749104025 scopus 로고    scopus 로고
    • for the use of a reversibly swithchable NHC- metal complex in the Kumada cross-coupling
    • e) V.W.-W. Yam, J. K.-W. Lee, C.-C. Ko, N. Zhu, J. Am. Chem. Soc. 2009, 131, 912; for the use of a reversibly swithchable NHC- metal complex in the Kumada cross-coupling
    • (2009) J. Am. Chem. Soc. , vol.131 , pp. 912
    • Yam, V.W.-W.1    Lee, J.K.-W.2    Ko, C.-C.3    Zhu, N.4
  • 170
    • 77956936123 scopus 로고    scopus 로고
    • during the preparation fo this manuscript an interesting publication on the derivatization of enolate-containing NHCs appeared
    • during the preparation fo this manuscript an interesting publication on the derivatization of enolate-containing NHCs appeared
  • 174
    • 77956922557 scopus 로고    scopus 로고
    • b) ref. [26]
    • b) ref. [26]
  • 175
    • 77956941919 scopus 로고    scopus 로고
    • It is obvious that a single parameter cannot represent all the complexity of the ligand structure, including its flexibility. Similarly, Tolman's cone angle method for the determination of the steric demand of phosphine also employs only one parameter, the cone angle θ'* d) It is important to note that the term "steric demand" of a ligand is not properly defined.
    • c) It is obvious that a single parameter cannot represent all the complexity of the ligand structure, including its flexibility. Similarly, Tolman's cone angle method for the determination of the steric demand of phosphine also employs only one parameter, the cone angle θ'* d) It is important to note that the term "steric demand" of a ligand is not properly defined.
  • 198
    • 77956941252 scopus 로고    scopus 로고
    • The X-ray data have been used for calculation.
    • The X-ray data have been used for calculation.
  • 204
    • 77956893305 scopus 로고    scopus 로고
    • e) ref. [44]
    • e) ref. [44]
  • 205
    • 77956939792 scopus 로고    scopus 로고
    • f) ref. [29d]
    • f) ref. [29d]
  • 209
    • 77956930693 scopus 로고    scopus 로고
    • b) ref. 37
    • b) ref. 37
  • 211
    • 77956912345 scopus 로고    scopus 로고
    • For the utilization of some ligands with flexible steric bulk in catalysis, see: a) ref. [46b, c]
    • For the utilization of some ligands with flexible steric bulk in catalysis, see: a) ref. [46b, c]
  • 216
    • 77956918597 scopus 로고    scopus 로고
    • d) ref. [24]
    • d) ref. [24]
  • 217
    • 77956911225 scopus 로고    scopus 로고
    • e) ref. [58].
    • e) ref. [58].


* 이 정보는 Elsevier사의 SCOPUS DB에서 KISTI가 분석하여 추출한 것입니다.