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A MECHANISTIC STUDY ON THE REACTIONS OF VINYL CARBENE WITH HYDROGEN, CARBON MONOXIDE AND CARBON DIOXIDE: SHED LIGHT ON FURTHER MANIPULATIONS

Yıl 2017, Cilt: 5 Sayı: 1, 91 - 99, 07.04.2017

Cem Burak Yıldız

https://doi.org/10.20290/aubtdb.287468

Öz

Density
Functional calculations (DFT) have been used to explore the potential energy
profiles of H2, CO, and CO2 activation reactions by vinyl
carbene structure 1. The reactions
of vinyl carbene 1 with CO2
was proposed to yield a variety of possible products (3−5) depending on
its selectivity. The DFT calculations established that the proposed reactions
of 1 with CO2 proceed
in a concerted or stepwise manners to form 3 and 5. However, that of CO reaction occur in only concerted
fashion for the proposed products 15 and 16. Furthermore, the compound 1 is found to be most reactive
than 5 and 16 towards H2 with the required lower energy
barrier. Finally, the most dominant routes are determined to be formation
processes of 3, 4, and 10.

Anahtar Kelimeler

Vinyl carbene Small molecule activation DFT CO CO2

Kaynakça

  • [1] Kirmse W. Carbene Chemistry, 2nd ed. New York, NY, USA: Academic Press, 1971.
  • [2] Gilchrist T. L. Carbenes and Nitrenes, in Organic Reaction Mechanisms. Chichester, UK: Wiley, 1972.
  • [3] Wentrup C. Reactive Molecules. New York, NY, USA: Wiley, 1984.
  • [4] Doyle MP, Forbes DC. Recent advances in asymmetric catalytic metal carbene transformations. Chem Rev 1998; 98: 911−935.
  • [5] Richard SG, Kevin RM. Recent advances in alkylidene carbene chemistry. Tetrahedron 2015; 71: 7795−7835.
  • [6] Ohira S, Sawamoto T, Yamato M. Synthesis of (−)−neplanocin A via C−H insertion of alkylidenecarbene. Tetrahedron Lett. 1995; 36: 1537−1538.
  • [7] Eisler S, Tykwinski RR. Migrating alkynes in vinylidene carbenoids:  An unprecedented route to polyynes. J Am Chem Soc. 2000; 122: 10736−10737.
  • [8] Van Nhien AN, León R, Postel D, Carreiras MC, García AG, Marco‐Contelles J.1,6‐C‐H and 1,5‐O‐Si insertion reactions of alkylidenecarbene derivatives of monosaccharides. J Carbohyd Chem. 2005; 24; 369–377.
  • [9] Tsai CC, Chien CT, Chang YC, Lin HC, Yan TH. Intramolecular C−H insertion by an alkylidene carbene: Diastereoselective Synthesis of a Taxol A Ring Synthon. J Org Chem. 2005; 70: 5745−5747.
  • [10] Satoh T. Recent advances in the chemistry of magnesium carbenoids. Chem Soc Rev. 2007; 36: 1561−1572.
  • [11] Satoh T. Recent Advances in the chemistry and synthetic uses of magnesium carbenoids. Heterocycles 2012; 85: 1−33.
  • [12] Quinodoz P, Wright K, Drouillat B, David O, Marrot J, Couty F. Synthesis of homopropargylamines from 2−cyanoazetidines. Chem Commun. 2016; 52: 10072−10075.
  • [13] Frihed TG, Bols M, Pedersen CM. C–H Functionalization on carbohydrates. European J Org Chem. 2016; 16: 2740−2756.
  • [14] Stang PJ. Unsaturated carbenes. Chem Rev 1978; 78: 383−405.
  • [15] Stang PJ, Fisk TE. Extended unsaturated carbenes. Generation and nature of alkadienylidenecarbenes. J Chem Soc 1980; 102; 6813−6816.
  • [16] P.J. Stang, J. Organomet. Chem. 46 (1981) 4585.
  • [17] Stang PJ, Bjork JA. Reaction of isopropylidenecarbene with isonitriles. Evidence for the formation of alkadienylideneamine. Chem Commun 1978; 23: 1057−1058.
  • [18] Brown RFC, Eastwood FW, Harrington KJ, McMullen GL. Methyleneketenes and methylenecarbenes. Aust J Chem. 1974; 27: 2393−2402.
  • [19] Feldman KS, Perkins AL. 1,6−C−H insertion of alkylidenecarbenes in 1−naphthol and 1−anthrol derivatives. Tetrahedron Lett. 2001; 42: 6031−6033.
  • [20] Bonomo L, Stern C, Solari E, Scopelliti R, Floriani C. Acetylenes rearranging on Ruthenium–Porphyrinogen and leading to vinylidene and carbene functionalities. Angew Chem Int Ed 2001: 40: 1449−1452.
  • [21] Ciardi, C.; Reginato, G.; Gonsalvi L, de los Rios I, Romerosa A, Peruzzini M. Ruthenium(II) π−alkyne and vinylidene complexes derived from glycoynitols:  New precursors for water−soluble unsaturated carbenes. Organometallics. 2004; 23: 2020−2026.
  • [22] Cheng CJ, Tong HC, Fong YH, Wang PY, Kuo YL, Lo YH, Lin CH. Reactions of Tp(NH=CPh2)(PPh3)Ru–Cl with HC≡CPh in the presence of H2O: insertion/hydration products Dalton Trans. 2009; 4435−4438.
  • [23] Ma ESF, Patrick BO, James BR. Reactions of phenylacetylene and p−tolylacetylene with a five−coordinate RuII complex. Inorg Chim Acta. 2013; 408: 126−130.
  • [24] Bucher J, Stoßer T, Rudolph M, Rominger F, Hashmi ASK. CO Extrusion in homogeneous gold catalysis: Reactivity of gold acyl species generated through water addition to gold vinylidenes. Angew Chem Int Ed 2015; 54: 1666−1670.
  • [25] Raubenheimer HG. Gold acyl complex formation and decarbonylation during indene synthesis from catalytically active vinylidene complexes. ChemCatChem. 2015; 7: 1261−1262.
  • [26] Apeloig Y, Karni M, Stang PJ, Fox DP. Transition−state geometries and stereoselectivity of alkylidenecarbene addition to olefins. An experimental and theoretical investigation. J Am Chem Soc 1983; 105: 4781−4792.
  • [27] Fox DP, Stang PJ, Apeloig Y, Karni M. Stereoselectivity of alkylidenecarbene addition to olefins. 2. Effect of orbital polarization in the alkenes. J Am Chem Soc 1986; 108: 750−756.
  • [28] Lu XH, Wang YX. Theoretical studies on mechanisms of cycloaddition reaction between dichlorovinylidene and formaldehyde:  Concerted and Stepwise? J Phys Chem A 2003; 107: 7885−7890.
  • [29] Lu XH, Wu WR, Yu HB, Yang XL, Xu YH. A theoretical study on the mechanism of cycloaddition reaction between vinylidene and acetone. J Mol Struct (Theochem) 2005; 755: 39−44.
  • [30] Lu XH, Yu HB, Wu WR, Xu YH., You have full text access to this contentTheoretical studies of mechanisms of cycloaddition reaction between difluoromethylene carbene and acetone. Int J Quantum Chem 2007; 107: 451−457.
  • [31] Lu XH, Xiang PP, Wu WR, Che X. Theoretical study on mechanism of cycloaddition reaction between dimethyl methylene carbene and ethylene. J Mol Struct (Theochem) 2008; 853: 82−88.
  • [32] Lu X, Lian Z, Li Y. An ab initio study of the mechanism of the cycloaddition reaction forming bicyclic compounds between vinylidene (H2C=C:) and ethylene. J Serb Chem Soc 2011: 76; 743–749.
  • [33] Frisch MJ, Trucks GW, Schlegel HB, Scuseria GE, Robb MA, Cheeseman JR, Montgomery Jr JA, Vreven T, Kudin K.N, Burant J.C, Millam J.M, Iyengar SS, Tomasi J, Barone V, Mennucci B, Cossi M, Scalmani G, Rega N, Petersson GA, Nakatsuji H, Hada M, Ehara M, Toyota K, Fukuda R, Hasegawa J, Ishida M, Nakajima T, Honda Y, Kitao O, Nakai H, Klene M, Li X, Knox JE, Hratchian HP, Cross JB, Bakken V, Adamo C, Jaramillo J, Gomperts R, Stratmann RE, Yazyev O, Austin AJ, Cammi R, Pomelli C, Ochterski JW, Ayala PY, Morokuma K, Voth GA, P Salvador, Dannenberg JJ, Zakrzewski VG, Dapprich S, Daniels AD, Strain MC, Farkas O, Malick DK, Rabuck AD, Raghavachari K, Foresman JB, Ortiz JV, Cui Q, Baboul AG, Clifford S, Cioslowski J, Stefanov BB, Liu G, Liashenko A, Piskorz P, Komaromi I, Martin RL, Fox DJ, Keith T, Al−Laham MA, Peng CY, Nanayakkara A, Challacombe M, Gill PMW, Johnson B, Chen W, Wong MW, Gonzalez C, Pople JA, Gaussian 03, Revision E.01, Gaussian 09, Inc: Wallingford CT, 2009.
  • [34] Becke AD. Density‐functional thermochemistry. III. The role of exact exchange. J Chem Phys 1993; 98: 5648−5652.
  • [35] Lee C, Yang W, Parr RG. Development of the Colle−Salvetti correlation−energy formula into a functional of the electron density. Phys Rev B 1998; 37: 785789.
  • [36] Gonzalez C, Schlegel HB. Improved algorithms for reaction path following: higher‐order implicit algorithms. J Chem Phys 1991; 95: 5853−5860.
  • [37] Wiberg KB. Application of the pople–santry–segal CNDO method to the cyclopropylcarbinyl and cyclobutyl cation and to bicyclobutane. Tetrahedron 1968; 24: 1083−1096.
  • [38] Dennington RII, Keith T, Millam J, Eppinnett K, Hovell WL, Gilliland R (2009) GaussView v.5.0.9 Visualizer and Builder. Gaussian 09. Wallingford, CT
  • [39] Wu CJ, Carter EA. Ab initio thermochemistry for unsaturated C2 hydrocarbons. J Phys Chem 1991; 95: 8352−8363.

A MECHANISTIC STUDY ON THE REACTIONS OF VINYL CARBENE WITH HYDROGEN, CARBON MONOXIDE AND CARBON DIOXIDE: SHED LIGHT ON FURTHER MANIPULATIONS

Yıl 2017, Cilt: 5 Sayı: 1, 91 - 99, 07.04.2017

Cem Burak Yıldız

https://doi.org/10.20290/aubtdb.287468

Öz

Density
Functional calculations (DFT) have been used to explore the potential energy
profiles of H2, CO, and CO2 activation reactions by vinyl
carbene structure 1. The reactions
of vinyl carbene 1 with CO2
was proposed to yield a variety of possible products (3−5) depending on
its selectivity. The DFT calculations established that the proposed reactions
of 1 with CO2 proceed
in a concerted or stepwise manners to form 3 and 5. However, that of CO reaction occur in only concerted
fashion for the proposed products 15 and 16. Furthermore, the compound 1 is found to be most reactive
than 5 and 16 towards H2 with the required lower energy
barrier. Finally, the most dominant routes are determined to be formation
processes of 3, 4, and 10.

Kaynakça

  • [1] Kirmse W. Carbene Chemistry, 2nd ed. New York, NY, USA: Academic Press, 1971.
  • [2] Gilchrist T. L. Carbenes and Nitrenes, in Organic Reaction Mechanisms. Chichester, UK: Wiley, 1972.
  • [3] Wentrup C. Reactive Molecules. New York, NY, USA: Wiley, 1984.
  • [4] Doyle MP, Forbes DC. Recent advances in asymmetric catalytic metal carbene transformations. Chem Rev 1998; 98: 911−935.
  • [5] Richard SG, Kevin RM. Recent advances in alkylidene carbene chemistry. Tetrahedron 2015; 71: 7795−7835.
  • [6] Ohira S, Sawamoto T, Yamato M. Synthesis of (−)−neplanocin A via C−H insertion of alkylidenecarbene. Tetrahedron Lett. 1995; 36: 1537−1538.
  • [7] Eisler S, Tykwinski RR. Migrating alkynes in vinylidene carbenoids:  An unprecedented route to polyynes. J Am Chem Soc. 2000; 122: 10736−10737.
  • [8] Van Nhien AN, León R, Postel D, Carreiras MC, García AG, Marco‐Contelles J.1,6‐C‐H and 1,5‐O‐Si insertion reactions of alkylidenecarbene derivatives of monosaccharides. J Carbohyd Chem. 2005; 24; 369–377.
  • [9] Tsai CC, Chien CT, Chang YC, Lin HC, Yan TH. Intramolecular C−H insertion by an alkylidene carbene: Diastereoselective Synthesis of a Taxol A Ring Synthon. J Org Chem. 2005; 70: 5745−5747.
  • [10] Satoh T. Recent advances in the chemistry of magnesium carbenoids. Chem Soc Rev. 2007; 36: 1561−1572.
  • [11] Satoh T. Recent Advances in the chemistry and synthetic uses of magnesium carbenoids. Heterocycles 2012; 85: 1−33.
  • [12] Quinodoz P, Wright K, Drouillat B, David O, Marrot J, Couty F. Synthesis of homopropargylamines from 2−cyanoazetidines. Chem Commun. 2016; 52: 10072−10075.
  • [13] Frihed TG, Bols M, Pedersen CM. C–H Functionalization on carbohydrates. European J Org Chem. 2016; 16: 2740−2756.
  • [14] Stang PJ. Unsaturated carbenes. Chem Rev 1978; 78: 383−405.
  • [15] Stang PJ, Fisk TE. Extended unsaturated carbenes. Generation and nature of alkadienylidenecarbenes. J Chem Soc 1980; 102; 6813−6816.
  • [16] P.J. Stang, J. Organomet. Chem. 46 (1981) 4585.
  • [17] Stang PJ, Bjork JA. Reaction of isopropylidenecarbene with isonitriles. Evidence for the formation of alkadienylideneamine. Chem Commun 1978; 23: 1057−1058.
  • [18] Brown RFC, Eastwood FW, Harrington KJ, McMullen GL. Methyleneketenes and methylenecarbenes. Aust J Chem. 1974; 27: 2393−2402.
  • [19] Feldman KS, Perkins AL. 1,6−C−H insertion of alkylidenecarbenes in 1−naphthol and 1−anthrol derivatives. Tetrahedron Lett. 2001; 42: 6031−6033.
  • [20] Bonomo L, Stern C, Solari E, Scopelliti R, Floriani C. Acetylenes rearranging on Ruthenium–Porphyrinogen and leading to vinylidene and carbene functionalities. Angew Chem Int Ed 2001: 40: 1449−1452.
  • [21] Ciardi, C.; Reginato, G.; Gonsalvi L, de los Rios I, Romerosa A, Peruzzini M. Ruthenium(II) π−alkyne and vinylidene complexes derived from glycoynitols:  New precursors for water−soluble unsaturated carbenes. Organometallics. 2004; 23: 2020−2026.
  • [22] Cheng CJ, Tong HC, Fong YH, Wang PY, Kuo YL, Lo YH, Lin CH. Reactions of Tp(NH=CPh2)(PPh3)Ru–Cl with HC≡CPh in the presence of H2O: insertion/hydration products Dalton Trans. 2009; 4435−4438.
  • [23] Ma ESF, Patrick BO, James BR. Reactions of phenylacetylene and p−tolylacetylene with a five−coordinate RuII complex. Inorg Chim Acta. 2013; 408: 126−130.
  • [24] Bucher J, Stoßer T, Rudolph M, Rominger F, Hashmi ASK. CO Extrusion in homogeneous gold catalysis: Reactivity of gold acyl species generated through water addition to gold vinylidenes. Angew Chem Int Ed 2015; 54: 1666−1670.
  • [25] Raubenheimer HG. Gold acyl complex formation and decarbonylation during indene synthesis from catalytically active vinylidene complexes. ChemCatChem. 2015; 7: 1261−1262.
  • [26] Apeloig Y, Karni M, Stang PJ, Fox DP. Transition−state geometries and stereoselectivity of alkylidenecarbene addition to olefins. An experimental and theoretical investigation. J Am Chem Soc 1983; 105: 4781−4792.
  • [27] Fox DP, Stang PJ, Apeloig Y, Karni M. Stereoselectivity of alkylidenecarbene addition to olefins. 2. Effect of orbital polarization in the alkenes. J Am Chem Soc 1986; 108: 750−756.
  • [28] Lu XH, Wang YX. Theoretical studies on mechanisms of cycloaddition reaction between dichlorovinylidene and formaldehyde:  Concerted and Stepwise? J Phys Chem A 2003; 107: 7885−7890.
  • [29] Lu XH, Wu WR, Yu HB, Yang XL, Xu YH. A theoretical study on the mechanism of cycloaddition reaction between vinylidene and acetone. J Mol Struct (Theochem) 2005; 755: 39−44.
  • [30] Lu XH, Yu HB, Wu WR, Xu YH., You have full text access to this contentTheoretical studies of mechanisms of cycloaddition reaction between difluoromethylene carbene and acetone. Int J Quantum Chem 2007; 107: 451−457.
  • [31] Lu XH, Xiang PP, Wu WR, Che X. Theoretical study on mechanism of cycloaddition reaction between dimethyl methylene carbene and ethylene. J Mol Struct (Theochem) 2008; 853: 82−88.
  • [32] Lu X, Lian Z, Li Y. An ab initio study of the mechanism of the cycloaddition reaction forming bicyclic compounds between vinylidene (H2C=C:) and ethylene. J Serb Chem Soc 2011: 76; 743–749.
  • [33] Frisch MJ, Trucks GW, Schlegel HB, Scuseria GE, Robb MA, Cheeseman JR, Montgomery Jr JA, Vreven T, Kudin K.N, Burant J.C, Millam J.M, Iyengar SS, Tomasi J, Barone V, Mennucci B, Cossi M, Scalmani G, Rega N, Petersson GA, Nakatsuji H, Hada M, Ehara M, Toyota K, Fukuda R, Hasegawa J, Ishida M, Nakajima T, Honda Y, Kitao O, Nakai H, Klene M, Li X, Knox JE, Hratchian HP, Cross JB, Bakken V, Adamo C, Jaramillo J, Gomperts R, Stratmann RE, Yazyev O, Austin AJ, Cammi R, Pomelli C, Ochterski JW, Ayala PY, Morokuma K, Voth GA, P Salvador, Dannenberg JJ, Zakrzewski VG, Dapprich S, Daniels AD, Strain MC, Farkas O, Malick DK, Rabuck AD, Raghavachari K, Foresman JB, Ortiz JV, Cui Q, Baboul AG, Clifford S, Cioslowski J, Stefanov BB, Liu G, Liashenko A, Piskorz P, Komaromi I, Martin RL, Fox DJ, Keith T, Al−Laham MA, Peng CY, Nanayakkara A, Challacombe M, Gill PMW, Johnson B, Chen W, Wong MW, Gonzalez C, Pople JA, Gaussian 03, Revision E.01, Gaussian 09, Inc: Wallingford CT, 2009.
  • [34] Becke AD. Density‐functional thermochemistry. III. The role of exact exchange. J Chem Phys 1993; 98: 5648−5652.
  • [35] Lee C, Yang W, Parr RG. Development of the Colle−Salvetti correlation−energy formula into a functional of the electron density. Phys Rev B 1998; 37: 785789.
  • [36] Gonzalez C, Schlegel HB. Improved algorithms for reaction path following: higher‐order implicit algorithms. J Chem Phys 1991; 95: 5853−5860.
  • [37] Wiberg KB. Application of the pople–santry–segal CNDO method to the cyclopropylcarbinyl and cyclobutyl cation and to bicyclobutane. Tetrahedron 1968; 24: 1083−1096.
  • [38] Dennington RII, Keith T, Millam J, Eppinnett K, Hovell WL, Gilliland R (2009) GaussView v.5.0.9 Visualizer and Builder. Gaussian 09. Wallingford, CT
  • [39] Wu CJ, Carter EA. Ab initio thermochemistry for unsaturated C2 hydrocarbons. J Phys Chem 1991; 95: 8352−8363.
Toplam 39 adet kaynakça vardır.

Ayrıntılar

Bölüm Araştırma Makalesi
Yazarlar

Cem Burak Yıldız

Yayımlanma Tarihi 7 Nisan 2017
Yayımlandığı Sayı Yıl 2017 Cilt: 5 Sayı: 1

Kaynak Göster

APA Yıldız, C. B. (2017). A MECHANISTIC STUDY ON THE REACTIONS OF VINYL CARBENE WITH HYDROGEN, CARBON MONOXIDE AND CARBON DIOXIDE: SHED LIGHT ON FURTHER MANIPULATIONS. Anadolu Üniversitesi Bilim Ve Teknoloji Dergisi - B Teorik Bilimler, 5(1), 91-99. https://doi.org/10.20290/aubtdb.287468
AMA Yıldız CB. A MECHANISTIC STUDY ON THE REACTIONS OF VINYL CARBENE WITH HYDROGEN, CARBON MONOXIDE AND CARBON DIOXIDE: SHED LIGHT ON FURTHER MANIPULATIONS. AUBTD-B. Nisan 2017;5(1):91-99. doi:10.20290/aubtdb.287468
Chicago Yıldız, Cem Burak. “A MECHANISTIC STUDY ON THE REACTIONS OF VINYL CARBENE WITH HYDROGEN, CARBON MONOXIDE AND CARBON DIOXIDE: SHED LIGHT ON FURTHER MANIPULATIONS”. Anadolu Üniversitesi Bilim Ve Teknoloji Dergisi - B Teorik Bilimler 5, sy. 1 (Nisan 2017): 91-99. https://doi.org/10.20290/aubtdb.287468.
EndNote Yıldız CB (01 Nisan 2017) A MECHANISTIC STUDY ON THE REACTIONS OF VINYL CARBENE WITH HYDROGEN, CARBON MONOXIDE AND CARBON DIOXIDE: SHED LIGHT ON FURTHER MANIPULATIONS. Anadolu Üniversitesi Bilim Ve Teknoloji Dergisi - B Teorik Bilimler 5 1 91–99.
IEEE C. B. Yıldız, “A MECHANISTIC STUDY ON THE REACTIONS OF VINYL CARBENE WITH HYDROGEN, CARBON MONOXIDE AND CARBON DIOXIDE: SHED LIGHT ON FURTHER MANIPULATIONS”, AUBTD-B, c. 5, sy. 1, ss. 91–99, 2017, doi: 10.20290/aubtdb.287468.
ISNAD Yıldız, Cem Burak. “A MECHANISTIC STUDY ON THE REACTIONS OF VINYL CARBENE WITH HYDROGEN, CARBON MONOXIDE AND CARBON DIOXIDE: SHED LIGHT ON FURTHER MANIPULATIONS”. Anadolu Üniversitesi Bilim Ve Teknoloji Dergisi - B Teorik Bilimler 5/1 (Nisan 2017), 91-99. https://doi.org/10.20290/aubtdb.287468.
JAMA Yıldız CB. A MECHANISTIC STUDY ON THE REACTIONS OF VINYL CARBENE WITH HYDROGEN, CARBON MONOXIDE AND CARBON DIOXIDE: SHED LIGHT ON FURTHER MANIPULATIONS. AUBTD-B. 2017;5:91–99.
MLA Yıldız, Cem Burak. “A MECHANISTIC STUDY ON THE REACTIONS OF VINYL CARBENE WITH HYDROGEN, CARBON MONOXIDE AND CARBON DIOXIDE: SHED LIGHT ON FURTHER MANIPULATIONS”. Anadolu Üniversitesi Bilim Ve Teknoloji Dergisi - B Teorik Bilimler, c. 5, sy. 1, 2017, ss. 91-99, doi:10.20290/aubtdb.287468.
Vancouver Yıldız CB. A MECHANISTIC STUDY ON THE REACTIONS OF VINYL CARBENE WITH HYDROGEN, CARBON MONOXIDE AND CARBON DIOXIDE: SHED LIGHT ON FURTHER MANIPULATIONS. AUBTD-B. 2017;5(1):91-9.
 Kapak Resmi İndir