Abstract
Frustrated Lewis pairs (FLPs) are the combination of Lewis acid and base motifs where steric hindrance prevents strong adduct formation. Accordingly, the ability of FLPs in small molecule activation and their capability in hydrogen cleavage led to their use in the hydrogenation of a wide range of unsaturated substrates. Here, we investigated theoretically the ability of three intramolecular phosphorus/boron FLPs as bifunctional catalysts in the metal-free hydrogenation of dimethylacetylene to cis-alkene. The mechanism of this hydrogenation reaction, based on the boron acceptor [including –OR substituents (B(OR)2), where R is an aliphatic or aromatic branch] and phosphorus donor, has been explored. Based on the results obtained, it was confirmed that the H2 splitting reaction and the formation of the phosphonium–borohydride motifs for these FLPs are endothermic. It has been shown that these FLPs have a moderate ability in H–H bond splitting. Also, the capability of the boron atom in FLPs on the hydrogenation reaction was investigated. The reduction steps of the mechanism showed an exothermic nature. This result revealed that the presence of the boron as a Lewis acid, with a very limited Lewis acidity, improves the catalytic hydrogenation reaction significantly. Finally, it was confirmed that the proposed FLPs in the cis-hydrogenation of alkynes will be effective.
Keywords
References
1.
Laurence C.
, and
Gal J.-F.
(2009 ) Lewis basicity and affinity scales: data and measurement. John Wiley & Sons , Hoboken, New Jersey .
2.
Brown H. C.
,
Schlesinger H.
, and
Cardon S. Z.
(1942 ) J. Am. Chem. Soc. , 64 , 325 .
3.
Welch G. C.
,
San Juan R. R.
,
Masuda J. D.
, and
Stephan D. W.
(2006 ) Science , 314 , 1124 .
4.
Stephan D. W.
(2013 ) In:
Erker G.
, and
Stephan D.W.
(eds), Frustrated Lewis pairs I, uncovering and understanding, Topics in Current Chemistry , Vol. 332 , Chap. 1, pp. 1 –44 . Springer-Verlag , Heidelberg .
5.
Stephan D. W.
, and
Erker G.
(2015 ) Angew. Chem., Int. Ed. , 54 , 6400 .
6.
Stephan D. W.
(2014 ) Acc. Chem. Res. , 48 , 306 .
7.
Voss T.
,
Mahdi T.
,
Otten E.
,
Frohlich R.
,
Kehr G.
,
Stephan D. W.
, and
Erker G.
(2012 ) Organometallics , 31 , 2367 .
8.
Herrington T. J.
,
Ward B. J.
,
Doyle L. R.
,
McDermott J.
,
White A. J. P.
,
Hunt P. A.
, and
Ashley A. E.
(2014 ) Chem. Commun. , 50 , 12753 .
9.
Chernichenko K.
,
Kótai B.
,
Pápai I.
,
Zhivonitko V.
,
Nieger M.
,
Leskelä M.
, and
Repo T.
(2015 ) Angew. Chem. , 127 , 1769 .
10.
Lawrence E. J.
,
Blagg R. J.
,
Hughes D. L.
,
Ashley A. E.
, and
Wildgoose G. G.
(2015 ) Chem.-Eur. J. , 21 , 900 .
11.
Zeonjuk L. L.
,
Petkov P. St.
,
Heine T.
,
Röschenthaler G.-V.
,
Eicher J.
, and
Vankova N.
(2015 ) Phys. Chem. Chem. Phys. , 17 , 10687 .
12.
Pérez P.
,
Yepes D.
,
Jaque P.
,
Chamorro E.
,
Domingo L. R.
,
Rojas R. S.
, and
Toro-Labbé A.
(2015 ) Phys. Chem. Chem. Phys. , 17 , 10715 .
13.
Pu M.
, and
Privalov T.
(2014 ) ChemPhysChem , 15 , 3714 .
14.
Skara G.
,
Pinter B.
,
Top J.
,
Geerlings P.
,
De Proft F.
, and
De Vleeschouwer F.
(2015 ) Chem.-Eur. J. , 21 , 5510 .
15.
Pu M.
, and
Privalov T.
(2014 ) ChemPhysChem , 15 , 2936 .
16.
Rokob T. A.
,
Bakó I.
,
Stirling A.
,
Hamza A.
, and
Pápai I.
(2013 ) J. Am. Chem. Soc. , 135 , 4425 .
17.
Lindqvist M.
,
Borre K.
,
Axenov K.
,
Kótai B.
,
Nieger M.
,
Leskelä M.
,
Pápai I.
, and
Repo T.
(2015 ) J. Am. Chem. Soc. , 137 , 4038 .
18.
Farrell J. M.
,
Posaratnanathan R. T.
, and
Stephan D. W.
(2015 ) Chem. Sci. , 6 , 2010 .
19.
Stennett T. E.
,
Pahl J.
,
Zijlstra H. S.
,
Seidel F. W.
, and
Harder S.
(2016 ) Organometallics , 35 , 207 .
20.
Waerder B.
,
Pieper M.
,
Körte L. A.
,
Kinder T. A.
,
Mix A.
,
Neumann B.
,
Stammler H.-G.
, and
Mitzel N. W.
(2015 ) Angew. Chem., Int. Ed. , 54 , 13416 .
21.
Oestreich M.
,
Hermeke J.
, and
Mohr J.
(2015 ) Chem. Soc. Rev. , 44 , 2202 .
22.
Ménard G.
, and
Stephan D. W.
(2012 ) Angew. Chem., Int. Ed. , 51 , 8272 .
23.
Neu R. C.
,
Ouyang E. Y.
,
Geier S. J.
,
Zhao X.
,
Ramos A.
, and
Stephan D. W.
(2010 ) Dalton Trans. , 39 , 4285 .
24.
Morgan M. M.
,
Marwitz A. J. V.
,
Piers W. E.
, and
Parvez M.
(2012 ) Organometallics , 32 , 317 .
25.
Rokob T. A.
,
Hamza A.
, and
Pápai I.
(2009 ) J. Am. Chem. Soc. , 131 , 10701 .
26.
Kronig S.
,
Theuergarten E.
,
Holschumacher D.
,
Bannenberg T.
,
Daniliuc C. G.
,
Jones P. G.
, and
Tamm M.
(2011 ) Inorg. Chem. , 50 , 7344 .
27.
Whittemore S. M.
,
Edvenson G.
,
Camaioni D. M.
,
Karkamkar A.
,
Neiner D.
,
Parab K.
, and
Autrey T.
(2015 ) Catal. Today , 251 , 28 .
28.
Stephan D. W.
,
Greenberg S.
,
Graham T. W.
,
Chase P.
,
Hastie J. J.
,
Geier S. J.
,
Farrell J. M.
,
Brown C. C.
,
Heiden Z. M.
,
Welch G. C.
, and
Ullrich M.
(2011 ) Inorg. Chem. , 50 , 12338 .
29.
Greb L.
,
Tussing S.
,
Schirmer B.
,
Oña-Burgos P.
,
Kaupmees K.
,
Lõkov M.
,
Leito I.
,
Grimme S.
, and
Paradies J.
(2013 ) Chem. Sci. , 4 , 2788 .
30.
Mahdi T.
,
Heiden Z. M.
,
Grimme S.
, and
Stephan D. W.
(2012 ) J. Am. Chem. Soc. , 134 , 4088 .
31.
Zhao J.
,
Wang G.
, and
Li S.
(2015 ) Dalton Trans. , 44 , 9200 .
32.
Gloriozov I.
, and
Oprunenko Y. F.
(2013 ) Moscow Univ. Chem. Bull. (Engl. Transl.) , 68 , 29 .
33.
Scott D. J.
,
Simmons T. R.
,
Lawrence E. J.
,
Wildgoose G. G.
,
Fuchter M. J.
, and
Ashley A. E.
(2015 ) ACS Catal. , 5 , 5540 .
34.
Gyömöre A.
,
Bakos M.
,
Földes T.
,
Pápai I.
,
Domján A.
, and
Soós T.
(2015 ) ACS Catal. , 5 , 5366 .
35.
Greb L.
,
Oña-Burgos P.
,
Schirmer B.
,
Grimme S.
,
Stephan D. W.
, and
Paradies J.
(2012 ) Angew. Chem. , 124 , 10311 .
36.
Segawa Y.
, and
Stephan D. W.
(2012 ) Chem. Commun. , 48 , 11963 .
37.
Hounjet L. J.
,
Bannwarth C.
,
Garon C. N.
,
Caputo C. B.
,
Grimme S.
, and
Stephan D. W.
(2013 ) Angew. Chem. , 125 , 7640 .
38.
Greb L.
,
Daniliuc C.-G.
,
Bergander K.
, and
Paradies J.
(2013 ) Angew. Chem., Int. Ed. , 52 , 5876 .
39.
Mahdi T.
, and
Stephan D. W.
(2015 ) Chem.-Eur. J. , 21 , 11134 .
40.
vom Stein T.
,
Peréz M.
,
Dobrovetsky R.
,
Winkelhaus D.
,
Caputo C. B.
, and
Stephan D. W.
(2015 ) Angew. Chem. , 127 , 10316 .
41.
Nishimura S.
(2001 ) Handbook of heterogeneous catalytic hydrogenation for organic synthesis. Wiley , New York .
42.
Clapham S. E.
,
Hadzovic A.
, and
Morris R. H.
(2004 ) Coord. Chem. Rev. , 248 , 2201 .
43.
Wang D.
, and
Astruc D.
(2015 ) Chem. Rev. , 115 , 6621 .
44.
Zuo W.
,
Lough A. J.
,
Li Y. F.
, and
Morris R. H.
(2013 ) Science , 342 , 1080 .
45.
Spielmann J.
,
Buch F.
, and
Harder S.
(2008 ) Angew. Chem. , 120 , 9576 .
46.
Corey E. J.
(2009 ) Angew. Chem., Int. Ed. , 48 , 2100 .
47.
Chernichenko K.
,
Lindqvist M.
,
Kótai B.
,
Nieger M.
,
Sorochkina K.
,
Pápai I.
, and
Repo T.
(2016 ) J. Am. Chem. Soc. , 138 , 4860 .
48.
Chernichenko K.
,
Madárasz A.
,
Pápai I.
,
Nieger M.
,
Leskela M.
, and
Repo T.
(2013 ) Nat. Chem. , 5 , 718 .
49.
Liu Y.
,
Hu L.
,
Chen H.
, and
Du H.
(2015 ) Chem.-Eur. J. , 21 , 3495 .
50.
Szeto K. C.
,
Sahyoun W.
,
Merle N.
,
Castelbou J. L.
,
Popoff N.
,
Lefebvre F.
,
Raynaud J.
,
Godard C.
,
Claver C.
,
Delevoye L.
,
Gauvin R. M.
, and
Taoufik M.
(2016 ) Catal. Sci. Technol. , 6 , 882 .
51.
Declercq R.
,
Bouhadir G.
,
Bourissou D.
,
Légare M.-A.
,
Courtemanche M.-A.
,
Nahi K. S.
,
Bouchard N.
,
Fontaine F.-G.
, and
Maron L.
(2015 ) ACS Catal. , 5 , 2513 .
52.
Frisch M. J.
,
Trucks G. W.
,
Schlegel H. B.
2009 ) Gaussian 09, revision A.01. Gaussian, Inc. , Wallingford, CT.
53.
Becke A. D.
(1993 ) J. Chem. Phys. , 98 , 5648 .
54.
Lee C.
,
Yang W.
, and
Parr R. G.
(1988 ) Phys. Rev. B: Condens. Matter Mater. Phys. , 37 , 785 .
55.
Vosko S. H.
,
Wilk L.
, and
Nusair M.
(1980 ) Can. J. Phys. , 58 , 1200 .
56.
Stephens P. J.
,
Devlin F. J.
,
Chabalowski C. F.
, and
Frisch M. J.
(1994 ) J. Phys. Chem. , 98 , 11623 .
57.
Becke A. D.
(1988 ) Phys. Rev. A: At., Mol., Opt. Phys. , 38 , 3098 .
58.
McLean A. D.
, and
Chandler G. S.
(1980 ) J. Chem. Phys. , 72 , 5639 .
59.
Salter E. A.
,
Trucks G. W.
, and
Bartlett R. J.
(1989 ) J. Chem. Phys. , 90 , 1752 .
60.
Peng C.
,
Ayala P. Y.
,
Schlegel H. B.
, and
Frisch M. J.
(1996 ) J. Comput. Chem. , 17 , 49 .
61.
Fukui K.
(1970 ) J. Phys. Chem. , 74 , 4161 .
62.
Reed A. E.
,
Curtiss L. A.
, and
Weinhold F.
(1988 ) Chem. Rev. , 88 , 899 .
63.
Reed A. E.
, and
Weinhold F.
(1983 ) J. Chem. Phys. , 78 , 4066 .
64.
Bader R. F.
(1990 ) Atoms in molecules: a quantum theory. Clarendon Press , Oxford .
65.
Henkelman G.
,
Arnaldsson A.
, and
Jónsson H.
(2006 ) Comput. Mater. Sci. , 36 , 354 .
66.
Bader R.
(2000 ) AIM2000 program. McMaster University , Hamilton, ON, Canada .
67.
Simón L.
, and
Goodman J. M.
(2011 ) Org. Biomol. Chem. , 9 , 689 .
68.
Sabet-Sarvestani H.
,
Eshghi H.
,
Bakavoli M.
,
Izadyar M.
, and
Rahimizadeh M.
(2014 ) RSC Adv. , 4 , 43485 .