Cationic iron(II) complexes of the mixed cyclopentadienyl (Cp) and the N-heterocyclic carbene (NHC) ligands as effective precatalysts for the hydrosilylation of carbonyl compounds

Dharmendra Kumar; A.P. Prakasham; Linus Paulin Bheeter; Jean Baptiste Sortais; Manoj Gangwar; Thierry Roisnel; Alok Ch Kalita; Christophe Darcel; Prasenjit Ghosh

doi:10.1016/j.jorganchem.2014.03.016

Cationic iron(II) complexes of the mixed cyclopentadienyl (Cp) and the N-heterocyclic carbene (NHC) ligands as effective precatalysts for the hydrosilylation of carbonyl compounds

Dharmendra Kumar, A.P. Prakasham, Linus Paulin Bheeter, Jean Baptiste Sortais, Manoj Gangwar, Thierry Roisnel, Alok Ch Kalita, Christophe Darcel, Prasenjit Ghosh

Research output: Contribution to journal › Article › Academic › peer-review

36 Citations (Scopus)

Abstract

A series of iron(II) complexes of N-heterocyclic carbene ligands was synthesized and fully structurally characterized. Specifically, the benzimidazole based {Cp[1,3-di-R-benzimidazol-2-ylidene]-Fe(CO)₂}I [R = Et (1b), i-Pr (2b) and n-Bu (3b)] and the imidazole based {Cp[1-benzyl-3-R-imidazol-2-ylidene]Fe(CO)₂}PF₆ [R = Me (4b) and Et (5b)] type of complexes were synthesized from their respective benzimidazolium iodide (1-3)a and their imidazolium hexafluorophosphate (4-5)a salts by the reaction with CpFe(CO)₂I in the presence of MN(SiMe ₃)₂ (M = Li or K) as a base. The molecular structures of the (1-5)b complexes reveal that the metal center display a conventional piano stool structure. More importantly, the (1-5)b complexes, when irradiated with visible light, effectively catalyzed the hydrosilylation reaction of carbonyl compounds namely, of the aldehyde and ketone substrates, using organosilane reagents. Specifically, the (1-5)b complexes performed the hydrosilylation of a representative benzaldehyde substrate using phenylsilane in ambient conditions at 30 °C while that of the representative acetophenone substrate at a more elevated temperature of 70°C. The benzimidazole derived complexes (1-3)b displayed superior activity than the imidazole derived (4-5)b complexes.

Original language	English
Pages (from-to)	81-87
Number of pages	7
Journal	Journal of Organometallic Chemistry
Volume	762
DOIs	https://doi.org/10.1016/j.jorganchem.2014.03.016
Publication status	Published - 15 Jul 2014
Externally published	Yes

Bibliographical note

Funding Information:
PG is grateful to the Sophisticated Analytical Instrument Facility at IIT Bombay, India, for the characterization data and thanks Prof. R. Murugavel for the use of his Single Crystal X-ray Diffraction Facility established through a DAE-SRC Outstanding Investigator Award. DK thanks CSIR-UGC, New Delhi, for research fellowship.

Funding Information:
We thank Indo-French Centre for the Promotion of Advanced Research – IFCPAR (Project No: 4605-B ), New Delhi, for financial support of this research.

Funding Information:
CD and JBS thank the French “ Ministère de l’Enseignement Supérieur et de la Recherche ” and the CNRS for financial support. LPB thanks IFCPAR for a PhD grant.

Funding

PG is grateful to the Sophisticated Analytical Instrument Facility at IIT Bombay, India, for the characterization data and thanks Prof. R. Murugavel for the use of his Single Crystal X-ray Diffraction Facility established through a DAE-SRC Outstanding Investigator Award. DK thanks CSIR-UGC, New Delhi, for research fellowship. We thank Indo-French Centre for the Promotion of Advanced Research – IFCPAR (Project No: 4605-B ), New Delhi, for financial support of this research. CD and JBS thank the French “ Ministère de l’Enseignement Supérieur et de la Recherche ” and the CNRS for financial support. LPB thanks IFCPAR for a PhD grant.

Keywords

Benzimidazole
Hydrosilylation
Imidazole
Iron
NHC ligands

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10.1016/j.jorganchem.2014.03.016

Cite this

Kumar, D., Prakasham, A. P., Bheeter, L. P., Sortais, J. B., Gangwar, M., Roisnel, T., Kalita, A. C., Darcel, C., & Ghosh, P. (2014). Cationic iron(II) complexes of the mixed cyclopentadienyl (Cp) and the N-heterocyclic carbene (NHC) ligands as effective precatalysts for the hydrosilylation of carbonyl compounds. Journal of Organometallic Chemistry, 762, 81-87. https://doi.org/10.1016/j.jorganchem.2014.03.016

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title = "Cationic iron(II) complexes of the mixed cyclopentadienyl (Cp) and the N-heterocyclic carbene (NHC) ligands as effective precatalysts for the hydrosilylation of carbonyl compounds",

abstract = "A series of iron(II) complexes of N-heterocyclic carbene ligands was synthesized and fully structurally characterized. Specifically, the benzimidazole based {Cp[1,3-di-R-benzimidazol-2-ylidene]-Fe(CO)2}I [R = Et (1b), i-Pr (2b) and n-Bu (3b)] and the imidazole based {Cp[1-benzyl-3-R-imidazol-2-ylidene]Fe(CO)2}PF6 [R = Me (4b) and Et (5b)] type of complexes were synthesized from their respective benzimidazolium iodide (1-3)a and their imidazolium hexafluorophosphate (4-5)a salts by the reaction with CpFe(CO)2I in the presence of MN(SiMe 3)2 (M = Li or K) as a base. The molecular structures of the (1-5)b complexes reveal that the metal center display a conventional piano stool structure. More importantly, the (1-5)b complexes, when irradiated with visible light, effectively catalyzed the hydrosilylation reaction of carbonyl compounds namely, of the aldehyde and ketone substrates, using organosilane reagents. Specifically, the (1-5)b complexes performed the hydrosilylation of a representative benzaldehyde substrate using phenylsilane in ambient conditions at 30 °C while that of the representative acetophenone substrate at a more elevated temperature of 70°C. The benzimidazole derived complexes (1-3)b displayed superior activity than the imidazole derived (4-5)b complexes.",

keywords = "Benzimidazole, Hydrosilylation, Imidazole, Iron, NHC ligands",

author = "Dharmendra Kumar and A.P. Prakasham and Bheeter, {Linus Paulin} and Sortais, {Jean Baptiste} and Manoj Gangwar and Thierry Roisnel and Kalita, {Alok Ch} and Christophe Darcel and Prasenjit Ghosh",

note = "Funding Information: PG is grateful to the Sophisticated Analytical Instrument Facility at IIT Bombay, India, for the characterization data and thanks Prof. R. Murugavel for the use of his Single Crystal X-ray Diffraction Facility established through a DAE-SRC Outstanding Investigator Award. DK thanks CSIR-UGC, New Delhi, for research fellowship. Funding Information: We thank Indo-French Centre for the Promotion of Advanced Research – IFCPAR (Project No: 4605-B ), New Delhi, for financial support of this research. Funding Information: CD and JBS thank the French “ Minist{\`e}re de l{\textquoteright}Enseignement Sup{\'e}rieur et de la Recherche ” and the CNRS for financial support. LPB thanks IFCPAR for a PhD grant. ",

year = "2014",

month = jul,

day = "15",

doi = "10.1016/j.jorganchem.2014.03.016",

language = "English",

volume = "762",

pages = "81--87",

journal = "Journal of Organometallic Chemistry",

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Kumar, D, Prakasham, AP, Bheeter, LP, Sortais, JB, Gangwar, M, Roisnel, T, Kalita, AC, Darcel, C & Ghosh, P 2014, 'Cationic iron(II) complexes of the mixed cyclopentadienyl (Cp) and the N-heterocyclic carbene (NHC) ligands as effective precatalysts for the hydrosilylation of carbonyl compounds', Journal of Organometallic Chemistry, vol. 762, pp. 81-87. https://doi.org/10.1016/j.jorganchem.2014.03.016

Cationic iron(II) complexes of the mixed cyclopentadienyl (Cp) and the N-heterocyclic carbene (NHC) ligands as effective precatalysts for the hydrosilylation of carbonyl compounds. / Kumar, Dharmendra; Prakasham, A.P.; Bheeter, Linus Paulin et al.
In: Journal of Organometallic Chemistry, Vol. 762, 15.07.2014, p. 81-87.

Research output: Contribution to journal › Article › Academic › peer-review

TY - JOUR

T1 - Cationic iron(II) complexes of the mixed cyclopentadienyl (Cp) and the N-heterocyclic carbene (NHC) ligands as effective precatalysts for the hydrosilylation of carbonyl compounds

AU - Kumar, Dharmendra

AU - Prakasham, A.P.

AU - Bheeter, Linus Paulin

AU - Sortais, Jean Baptiste

AU - Gangwar, Manoj

AU - Roisnel, Thierry

AU - Kalita, Alok Ch

AU - Darcel, Christophe

AU - Ghosh, Prasenjit

N1 - Funding Information: PG is grateful to the Sophisticated Analytical Instrument Facility at IIT Bombay, India, for the characterization data and thanks Prof. R. Murugavel for the use of his Single Crystal X-ray Diffraction Facility established through a DAE-SRC Outstanding Investigator Award. DK thanks CSIR-UGC, New Delhi, for research fellowship. Funding Information: We thank Indo-French Centre for the Promotion of Advanced Research – IFCPAR (Project No: 4605-B ), New Delhi, for financial support of this research. Funding Information: CD and JBS thank the French “ Ministère de l’Enseignement Supérieur et de la Recherche ” and the CNRS for financial support. LPB thanks IFCPAR for a PhD grant.

PY - 2014/7/15

Y1 - 2014/7/15

N2 - A series of iron(II) complexes of N-heterocyclic carbene ligands was synthesized and fully structurally characterized. Specifically, the benzimidazole based {Cp[1,3-di-R-benzimidazol-2-ylidene]-Fe(CO)2}I [R = Et (1b), i-Pr (2b) and n-Bu (3b)] and the imidazole based {Cp[1-benzyl-3-R-imidazol-2-ylidene]Fe(CO)2}PF6 [R = Me (4b) and Et (5b)] type of complexes were synthesized from their respective benzimidazolium iodide (1-3)a and their imidazolium hexafluorophosphate (4-5)a salts by the reaction with CpFe(CO)2I in the presence of MN(SiMe 3)2 (M = Li or K) as a base. The molecular structures of the (1-5)b complexes reveal that the metal center display a conventional piano stool structure. More importantly, the (1-5)b complexes, when irradiated with visible light, effectively catalyzed the hydrosilylation reaction of carbonyl compounds namely, of the aldehyde and ketone substrates, using organosilane reagents. Specifically, the (1-5)b complexes performed the hydrosilylation of a representative benzaldehyde substrate using phenylsilane in ambient conditions at 30 °C while that of the representative acetophenone substrate at a more elevated temperature of 70°C. The benzimidazole derived complexes (1-3)b displayed superior activity than the imidazole derived (4-5)b complexes.

AB - A series of iron(II) complexes of N-heterocyclic carbene ligands was synthesized and fully structurally characterized. Specifically, the benzimidazole based {Cp[1,3-di-R-benzimidazol-2-ylidene]-Fe(CO)2}I [R = Et (1b), i-Pr (2b) and n-Bu (3b)] and the imidazole based {Cp[1-benzyl-3-R-imidazol-2-ylidene]Fe(CO)2}PF6 [R = Me (4b) and Et (5b)] type of complexes were synthesized from their respective benzimidazolium iodide (1-3)a and their imidazolium hexafluorophosphate (4-5)a salts by the reaction with CpFe(CO)2I in the presence of MN(SiMe 3)2 (M = Li or K) as a base. The molecular structures of the (1-5)b complexes reveal that the metal center display a conventional piano stool structure. More importantly, the (1-5)b complexes, when irradiated with visible light, effectively catalyzed the hydrosilylation reaction of carbonyl compounds namely, of the aldehyde and ketone substrates, using organosilane reagents. Specifically, the (1-5)b complexes performed the hydrosilylation of a representative benzaldehyde substrate using phenylsilane in ambient conditions at 30 °C while that of the representative acetophenone substrate at a more elevated temperature of 70°C. The benzimidazole derived complexes (1-3)b displayed superior activity than the imidazole derived (4-5)b complexes.

KW - Benzimidazole

KW - Hydrosilylation

KW - Imidazole

KW - Iron

KW - NHC ligands

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U2 - 10.1016/j.jorganchem.2014.03.016

DO - 10.1016/j.jorganchem.2014.03.016

M3 - Article

AN - SCOPUS:84899674953

SN - 0022-328X

VL - 762

SP - 81

EP - 87

JO - Journal of Organometallic Chemistry

JF - Journal of Organometallic Chemistry

ER -

Cationic iron(II) complexes of the mixed cyclopentadienyl (Cp) and the N-heterocyclic carbene (NHC) ligands as effective precatalysts for the hydrosilylation of carbonyl compounds

Abstract

Bibliographical note

Funding

Keywords

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