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Chemical Science
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ARTICLE
5 a) Y. Peng, M. Brynda, B. D. Ellis, J. C. Fettinger, E. Rivard and
Journal Name
P. P. Power, Chem. Commun., 2008, 45, 6042; b) Z. Zhu, X.
Wang, Y. Peng, H Lei, J. C Fettinger, E. Rivard and P. P. Power,
Angew. Chem. Int. Ed., 2009, 48, 2031; c) K. Nagata, T.
Murosaki, T. Agou, T. Sasamori, T. Matsuo and N. Tokitoh,
Angew. Chem. Int. Ed., 2016, 55, 12877; d) A. Rit, J. Campos,
reversible behaviour of R2Sn in thDisOI:w10o.1r0k39/isC8SliCk0e3ly110J
a
consequence of the weaker Sn-H vs Si-H bond strength,
which renders the thermodynamics of RE more favourable
(see ref. 6d).
H. Niu and S. Aldridge, Nat. Chem., 2016, 8, 1022; e) T. Kosai 18 a) K. W. Zilm, G. A. Lawless, R. M. Merrill, J. M. Millar and G.
and T. Iwamoto, J. Am. Chem. Soc., 2017, 139, 18146; f) D.
Wendel, T. Szilvási, C. Jandl, S. Inoue and B. Rieger, J. Am.
Chem. Soc., 2017, 139, 9156.
G. Webb, J. Am. Chem. Soc., 1987, 109, 7236; b) R. Sedlak, O.
A. Stasyuk, C. Fonseca Guerra, J. Řezáč, A. Růžička and P.
Hobza, J. Chem. Theory Comput., 2016, 12, 1696.
6
a) G. D. Frey, V. Lavallo, B. Donnadieu, W. W. Schoeller and 19 The 119Sn NMR resonance for
1
can only be observed in
G. Bertrand, Science, 2007, 316, 439; b) Y. Peng, J. D. Guo, B.
D. Ellis, Z. Zhu, J. C. Fettinger, S. Nagase and P. P. Power, J.
Am. Chem. Soc., 2009, 131, 16272; c) A. V. Protchenko, K. H.
Birjkumar, D. Dange, A. D. Schwarz, D. Vidovic, C. Jones, N.
Kaltsoyannis, P. Mountford and S. Aldridge, J. Am. Chem.
Soc., 2012, 134, 6500; d) A. V. Protchenko, J. I. Bates, L. M. A.
dilute samples and at high temperature (T > 345 K), while
that for [
1
]
can only be resolved at T < 225 K. At
intermediate2 temperatures no signal is observable, which
prevents an assessment of interaction between the two tin
species and Et3N using 119Sn NMR under relevant reaction
conditions. See reference 18a.
Saleh, M. P. Blake, A. D. Schwarz, E. L. Kolychev, A. L. 20 A 1:2:3:2:1 multiplet was also observed in the 119Sn NMR
Thompson, C. Jones, P. Mountford and S. Aldridge, J. Am.
Chem. Soc., 2016, 138, 4555; e) D. Wendel, A. Porzelt, F. A. 21 a) L. Rocchigiani, G. Ciancaleoni, C. Zuccaccia and A.
spectrum from 1J(119Sn-2H) coupling. See Fig. S3 in ESI.
D. Herz, D. Sarkar, C. Jandl, S. Inoue and B. Rieger, J. Am.
Chem. Soc., 2017, 139, 8134.
MacChioni, J. Am. Chem. Soc., 2014, 136, 112; b) T. A. Rokob,
A. Hamza, A. Stirling, T. Soós and I. Pápai, Angew. Chem. Int.
Ed., 2008, 47, 2435.
7
8
9
First example of FLP-mediated H2 heterolysis: G. C. Welch, R.
R. San Juan, J. D. Masuda and D. W. Stephan, Science, 2006, 22 A. Y. Houghton and T. Autrey, J. Phys. Chem. A, 2017, 121
314, 1124.
For a review detailing the scope of MG LAs in FLP chemistry 23 J. Burés, Angew. Chem. Int. Ed., 2016, 55, 2028.
see: S. A. Weicker and D. W. Stephan, Bull. Chem. Soc. Jpn., 24 E. Brunner, J. Chem. Eng. Data, 1985, 30, 269.
2015, 88, 1003.
For FLP H2 activation mediated by a Sn LA see: D. J. Scott, N.
A. Phillips, J. S. Sapsford, A. C. Deacy, M. J. Fuchter and A. E. 26 Assuming the same rate law applies. Supported by
,
8785.
25 Fitting the data to a model based on [
plots (see ESI for further details).
1]2 gave non-linear
Ashley, Angew. Chem. Int. Ed., 2016, 55, 14738;
10 a) D. W. Stephan, S. Greenberg, T. W. Graham, P. Chase, J. J. 27 T. M. Alligrant and J. C. Alvarez, J. Phys. Chem. C, 2011, 115
Hastie, S. J. Geier, J. M. Farrell, C. C. Brown, Z. M. Heiden, G. 10797.
C. Welch and M. Ullrich, Inorg. Chem., 2011, 50, 12338; b) D. 28 I. Kaljurand, A. Kütt, L. Sooväli, T. Rodima, V. Mäemets, I.
computational calculations.
,
J. Scott, M. J. Fuchter and A. E. Ashley, Chem. Soc. Rev., 2017,
46, 5689.
Leito and I. A. Koppel, J. Org. Chem., 2005, 70, 1019.
29 T. A. Rokob, A. Hamza and I. Pápai, J. Am. Chem. Soc., 2009,
131, 10701.
11 a) A. Y. Houghton, V. A. Karttunen, W. E. Piers and H. M.
Tuononen, Chem. Commun., 2014, 50, 1295; b) E. von 30 Et3N and DMAP: Z. Glasovac, M. Eckert-Maksić and Z. B.
Grotthuss, M. Diefenbach, M. Bolte, H. W. Lerner, M. C.
Maksić, New J. Chem., 2009, 33, 588; PMP: M. Dworniczak
and K. T. Leffeck, Can. J. Chem, 1990, 68, 1657; DBU and
TBTMG: C. F. Lemaire, J. J. Aerts, L. C. Libert, F. Mercier, D.
Goblet, A. R. Plenevaux and A. J. Luxen, Angew. Chem. Int.
Ed., 2010, 49, 3161.
Holthausen and M. Wagner, Angew. Chem. Int. Ed., 2016, 55
14067.
,
12 A. Hinz, A. Schulz and A. Villinger, Angew. Chem. Int. Ed.,
2016, 55, 12214.
13 S. Wang, T. J. Sherbow, L. A. Berben and P. P. Power, J. Am. 31 The energy values reported correspond to solution phase
Chem. Soc., 2018, 140, 590.
Gibbs free energies that are based on ωB97X-D/Def2TZVPP
electronic energies, and all additional terms obtained at the
ωB97X-D/Def2SVP level. See ESI for full computational
details.
14 a) H. G. Kuivila, A. K. Sawyer and A. G. Armour, J. Org. Chem.,
1961, 26, 1426; b) W. P. Neumann and K. König, Justus
Liebigs Ann. Chem., 1964, 677, 1; c) W. P. Neumann and K.
König, Justus Liebigs Ann. Chem., 1964, 677, 12.
32 In FLPs with early TSs, such as Mes3P/B(C6F5)3, a KIE of only
1.1 has been obtained (see ref. 22).
15 a) C. P. Sindlinger, A. Stasch, H. F. Bettinger and L.
Wesemann, Chem. Sci., 2015, 6, 4737; b) J.-J. Maudrich, C. P.
Sindlinger, F. S. W. Aicher, K. Eichele, H. Schubert and L.
Wesemann, Chem. Eur. J., 2017, 23, 2192; c) C. P. Sindlinger
and L. Wesemann, Chem. Sci., 2014,
5, 2739; d) C. P.
Sindlinger, W. Grahneis, F. S. W. Aicher and L. Wesemann,
Chem. Eur. J., 2016, 22, 7554; e) J. Klösener, M. Wiesemann,
M. Niemann, B. Neumann, H.-G. Stammler and B. Hoge,
Chem. Eur. J., 2018, 24, 4412.
16 a) P. J. Davidson, D. H. Harris and M. F. Lappert, J. Chem. Soc.
Dalt. Trans., 1976, 21
, 2268; b) The OA of reactive
heteropolar and homopolar bonds (e.g. alkyl halides, Br2) has
been documented: i) M. J. S. Gynane, M. F. Lappert, S. J.
Miles, A. J. Carty and N. J. Taylor, J. Chem. Soc., Dalton
Trans., 1977, 2009; b) J. D. Cotton, P. J. Davidson and M. F.
Lappert, J. Chem. Soc., Dalton Trans., 1976, 2275.
17 A cyclic dialkylsilylene, R’2Si, has been shown to act as either
a LA or LB to activate H2 in partnership with other LBs/LAs,
forming R’2SiH2. However, this reaction was irreversible; see
6 | J. Name., 2012, 00, 1-3
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