Please do not adjust margins
Catalysis Science & Technology
Page 12 of 14
ARTICLE
Journal Name
2017, 22, 615; (d) J.-T. Yu, F. Teng and J. Cheng, Adv. Synth.
Duhayon, J.-P. Majoral and V. CadiernDoO, IG: 1r0e.e10n39C/hDe0mCY.,020052133A,
15, 2447; (e) E. Tomás-Mendivil, R. García-Álvarez, C. Vidal,
Catal., 2017, 359, 26.
7
The reverse process, i.e. the dehydration of ureas, can also
be employed for the preparation of cyanamides. However,
the most prevalent methods for the synthesis of both mono-
and disubstituted cyamanides are (i) the direct alkylation of
sodium, potassium or calcium cyanamide and (ii) the
electrophilic cyanation of primary or secondary amines. In
addition, severe reaction conditions are usually required to
achieve the dehydration of ureas (see ref. 6).
P. Crochet and V. Cadierno, ACS Catal., 2014,
González-Fernández, P. J. González-Liste, J. Borge, P. Crochet
and V. Cadierno, Catal. Sci. Technol., 2016, , 4398; (g) E.
4, 1901; (f) R.
6
Tomás-Mendivil, J. Francos, R. González-Fernández, P. J.
González-Liste, J. Borge and V. Cadierno, Dalton Trans., 2016,
45, 13590; (h) R. González-Fernández, P. Crochet and V.
Cadierno, Org. Lett., 2016, 18, 6164.
8
For reviews covering the catalytic hydration of nitriles, see:
(a) V. Y. Kukushkin and A. J. L. Pombeiro, Chem. Rev., 2002, 16 (a) E. Tomás-Mendivil, V. Cadierno, M. I. Menéndez and R.
102, 1771; (b) V. Y. Kukushkin and A. J. L. Pombeiro, Inorg.
Chim. Acta, 2005, 358, 1; (c) T. J. Ahmed, S. M. M. Knapp and
D. R. Tyler, Coord. Chem. Rev., 2011, 255, 949; (d) R. García-
López, Chem. Eur. J., 2015, 21, 16874; (b) R. González-
Fernández, P. Crochet, V. Cadierno, M. I. Menéndez and R.
López, Chem. Eur. J., 2017, 23, 15210.
Álvarez, P. Crochet and V. Cadierno, Green Chem., 2013, 15
46; (e) R. García-Álvarez, J. Francos, E. Tomás-Mendivil, P.
Crochet and V. Cadierno, J. Organomet. Chem., 2014, 771
93; (f) E. L. Downs and D. R. Tyler, Coord. Chem. Rev., 2014,
280, 28; (g) V. Cadierno, Appl. Sci., 2015,
,
17 The utility of complex [RuCl2(η6-p-cymene)(PMe2OH)]
(1)
had been previously demonstrated by Tyler and co-workers:
S. M. M. Knapp, T. J. Sherbow, R. B. Yelle, J. J. Juliette and D.
R. Tyler, Organometallics, 2013, 32, 3744.
,
5
, 380; (h) M. A. 18 A similar mechanism was also proposed for the well-known
Hussain and J. W. Kim, Appl. Chem. Eng., 2015, 26, 128; (i)
M.-X. Wang, Acc. Chem. Res., 2015, 48, 602; (j) K. Singh, A.
Sarbaina and J. K. Bera, J. Indian Chem. Soc., 2018, 95, 853.
Parkins platinum catalyst [PtH{(PMe2O)2H}(PMe2OH)]: (a) T.
Ghaffar, A. W. Parkins, Tetrahedron Lett., 1995, 36, 8657; (b)
J. Mol. Catal. A: Chem., 2000, 160, 249.
9
For illustrative examples, see: (a) E. B. Vliet, J. Am. Chem. 19 The non-innocent role of phosphinous acids R2POH in other
Soc., 1924, 46, 1305; (b) T. Mukaiyama, S. Ohishi and H.
Takamura, Bull. Chem. Soc. Jpn., 1954, 27, 416; (c) Y. L. Chow
and K. E. Haque, Can. J. Chem., 1968, 46, 2901; (d) S. Nag, G.
P. Yadav, P. R. Maulik and S. Batra, Synthesis, 2007, 911; (e)
V. D. Jadhav, E. Herdtweck and F. P. Schmidtchen, Chem. Eur.
J., 2008, 14, 6098.
catalytic transformations, such as Ru-catalyzed C-H bond
activation and C=C bond isomerization processes, has also
been documented. See, for example: (a) A. Gallen, A. Riera,
X. Verdaguer and A. Grabulosa, Catal. Sci. Technol., 2019,
5504; (b) J. Francos, D. Elorriaga, P. Crochet and V. Cadierno,
Coord. Chem. Rev., 2019, 387 199; (c) R. González-
9,
,
10 (a) N. Nasrollahzadeh, RSC Adv., 2014,
4
, 29089; (b) Z.
Fernández, P. Crochet and V. Cadierno, Organometallics,
2019, 38, 3696.
Issaabadi, N. Nasrollahzadeh and S. M. Sajadi, J. Colloid
Interface Sci., 2017, 503, 57; (c) D. Habibi, S. Heydari, A. 20 (a) T. J. Geldbach, D. Drago and P. S. Pregosin, J. Organomet.
Faraji, H. Keypour and M. Mahmoudabadi, Polyhedron, 2018,
151, 520; (d) S. S. Momeni, N. Nasrollahzadeh, A. Rustaiyan,
J. Colloid Interface Sci., 2017, 499, 93.
Chem., 2002, 643-644
Menéndez-Rodríguez, J. Francos, P. Crochet and V. Cadierno,
RSC Adv., 2014, , 63466.
, 214; (b) E. Tomás-Mendivil, L.
4
11 Alternative protocols for the hydration of cyanamides in 21 (a) J. I. Steinfeld, J. S. Francisco and W. L. Hase, in Chemical
organic media, employing acetaldoxime as a water surrogate
and catalytic systems based on InCl3, nano CeO2 and CuO
nanoparticles, have also appeared: (a) S. H. Kim, B. R. Park
and J. N. Kim, Bull. Korean Chem. Soc., 2011, 32, 716; (b) S.
Kinetics and Dynamics, 2nd Ed., Prentice Hall, New Jersey,
1999; (b) The inverse of the rate constant determined in
accordance with the thermodynamic formulation of TST
gives an estimate of how long a given reaction takes.
M. Sajadi and M. Maham, J. Chem. Res., 2013, 37, 623; (c) N. 22 J. A. Pople, Rev. Mod. Phys., 1999, 71, 1267.
Nasrollahzadeh, M. Maham and S. M. Sajadi, J. Colloid 23 (a) R. F. W. Bader, in Atoms in Molecules. A Quantum Theory,
Interface Sci., 2015, 455, 245.
University Press: Oxford, 1990; (b) R. F. W. Bader, Chem.
Rev., 1991, 91, 893; (c) R. F. W. Bader, P. L. A. Popelier and T.
A. Keith, Angew. Chem. Int. Ed., 1994, 33, 620.
12 Contrary to the case of simple carbonitriles (see reference
8i), no general protocols for the enzymatic hydration of
cyanamides are currently available. Only the conversion of 24 (a) X. Fradera, M. A. Austen, R. F. W. Bader, J. Phys. Chem. A,
unsubstituted cyanamide into urea catalyzed by some
particular enzymes has been described: (a) U. H. Maier-
1999, 103, 304; (b) X. Fradera, J. Poater, S. Simon, M. Durán,
M. Solá, Theor. Chem. Acc., 2002, 108, 214.
Greiner, B. M. Obermaier-Skrobranek, L. M. Estermaier, W. 25 (a) F. Weinhold and C. R. Landis, in Valency and Bonding: A
Kammerloher, C. Freund, C. Wülfing, U. I. Burkert, D. H.
Matern, M. Breuer and M. Eulitz, Proc. Natl. Acad. Sci. U.S.A.,
1991, 88, 4260; (b) F. Briganti, S. Mangani, A. Scozzafava, G.
Natural Bond Orbital Donor-Acceptor Perspective, Cambridge
University Press, Cambridge, 2005; (b) NBO, Version 3.1, E. D.
Glendening, A. E. Reed, J. E. Carpenter and F. Weinhold,
University of Wisconsin, Madison, WI, 2012.
Vernaglione and C. T. Supuran, J. Biol. Inorg. Chem., 1999, 4,
528; (c) A. Guerri, F. Briganti, A. Scozzafava, C. T. Supuran 26 N. A. Bokach, M. Haukka, P. Hirva, M. F. C. G. D. Silva, V. Y.
and S. Mangani, Biochemistry, 2000, 39, 12391; (d) J. Li, M.
Biss, Y. Fu, X. Xu, S. A. Moore and W. Xiao, J. Biol. Chem.,
2015, 290, 12664.
Kukushkin and A. J. L. Pombeiro, J. Organomet. Chem., 2006,
691, 2368.
27 For examples involving other cyanamides, see: (a) G.
Albertin, S. Antoniutti and J. Castro, Eur. J. Inorg. Chem.,
2009, 5352; (b) G. Albertin, S. Antoniutti, S. Caia and J.
Castro, Dalton Trans., 2014, 43, 7314.
28 The computed species 1-OH-S_M show M-Nnitrile-Cnitrile and
Nnitrile-Cnitrile-R bond angles very similar to those found in the
X-ray crystal structures of 5a and 5b, as they range from
176.9 to 178.6° and from 176.6 to 179.4°, respectively. As
nicely discussed in ref. 13a, a significant contribution of the
bent resonance form in a metal-coordinated cyanamide
should lead to M-Nnitrile-Cnitrile angles < 170°. The negligible
13 (a) N. A. Bokach and V. Y. Kukushkin, Coord. Chem. Rev.,
2013, 257, 2293 and references cited therein; (b) P. Tong, D.
Yang, Y. Li, B. Wang and J. Qu, Organometallics, 2015, 34
3571.
,
14 A. S. Smirnov, E. S. Butukhanova, N. A. Bokach, G. L. Starova,
V. V. Gurzhiy, M. L. Kuznetsov and V. Y. Kukushkin, Dalton
Trans., 2014, 43, 15798.
15 See, for example: (a) V. Cadierno, J. Díez, J. Francos and J.
Gimeno, Chem. Eur. J., 2010, 16, 9808; (b) E. Tílvez, M. I.
Menéndez and R. López, Organometallics, 2012, 31, 1618; (c)
12 | J. Name., 2012, 00, 1-3
This journal is © The Royal Society of Chemistry 20xx
Please do not adjust margins