ChemComm
DOI: 10.1039/C4CC06992G
a
Université de Toulouse, UPS, LHFA, 118 route de Narbonne, 31062
G. Fontaine, Chem. Commun., 2011, 47, 11131. (b) J. Boudreau, M.
A. Courtemanche, V. M. Marx, D. J. Burnell and F. G. Fontaine,
Chem. Commun., 2012, 48, 11250. (c) F. Bertini, F. Hoffmann, C.
Appelt, W. Uhl, A. W. Ehlers, J. C. Slootweg, and K. Lammertsma,
Organometallics, 2013, 32, 6764.
Toulouse, France, and CNRS, LHFA, UMR 5069, 31062 Toulouse,
France. Fax: 33 (0)5 61 55 82 04; Tel: 33 (0)5 61 55 68 03; E-mail:
bouhadir@chimie.ups-tlse.fr, dbouriss@chimie.ups-tlse.fr
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Department of Chemistry and Pharmaceutical Sciences, VU University
Amsterdam, De Boelelaan 1083, 1081 HV Amsterdam, The Netherlands.
E-mail: j.c.slootweg@vu.nl
Institut für Anorganische und Analytische Chemie der Westfälischen
12 By analogy with that observed upon reaction of PAl with small
molecules, the participation of both
coordination is associated with large JPH coupling constants (> 30
Hz) between the P atom and olefinic proton.
P and Al atoms upon
c
3
Wilhelms-Universität Münster, Corrensstrasse 30, 48149 Münster,
Germany. E-mail: uhlw@uni-muenster.de
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13 According to Cambridge Database searches, the average length of
terminal Cl–Al bonds is 2.21 Å and the lengths of Cl–Al bonds in
d
Université Paul Sabatier, Institut de Chimie de Toulouse (FR 2599), 118
route de Narbonne, 31062 Toulouse cedex 9, France.
bridging R
value = 2.37 Å).
Electronic Supplementary Information (ESI) available: Experimental 85 14 (a) S. Bontemps, G. Bouhadir, K. Miqueu, and D. Bourissou, J. Am.
3
Al−Cl–TM complexes range from 2.26 to 2.9 Å (mean
†
details and characterization data, including crystallographic data for 2ꢀ4;
computational studies. See DOI: 10.1039/b000000x/
Chem. Soc., 2006, 128, 12056. (b) S. Bontemps, G. Bouhadir, D. C.
Apperley, P. W. Dyer, K. Miqueu, and D. Bourissou, Chem. Asian J.,
2
009, 4, 428.
2
1
5
JPP coupling constants in linear gold(I) complexes featuring two
1
(a) I. Kuzu, I. Krummenacher, J. Meyer, F. Armbruster, and F.
Breher, Dalton Trans., 2008, 5836. (b) F. G. Fontaine, J. Boudreau,
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Bouhadir, A. Amgoune, and D. Bourissou, Adv. Organomet. Chem.,
90
95
different phosphines typically range from 250 to 350 Hz. For
representative examples, see : (a) N. S. Townsend, M. Green, and C.
A. Russell, Organometallics, 2012, 31, 2543. (b) M. Bardaji, P. G.
Jones, A. Laguna, M. D. Villacampa, and N. Villaverde, Dalton
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Ely, Inorg. Chem., 2005, 44, 3275.
2
010, 58, 1. (d) D. J. H. Emslie, B. E. Cowie, and K. B. Kolpin,
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A. Amgoune and D. Bourissou, Chem. Commun., 2011, 47, 859.
(a) H. Kameo and H. Nakazawa, Organometallics, 2012, 31, 7476.
16 According to a Cambridge database search, the average AlCl distance
–
3
in chloroaluminates (R AlCl) is 2.209 Å.
+
(b) G. R. Owen, Chem. Soc. Rev., 2012, 41, 3535. (c) W. H. Harman
17 A few [(phosphine)Au(tht)] complexes are known. They were all
obtained by reaction of the corresponding (phosphine)AuCl
complexes with silver salts in the presence of tht: (a) S. Doherty, J.
G. Knight, A. S. Hashmi, C. H. Smyth, N. A. B. Ward, K. J. Robson,
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K. J. Robson, and F. Rominger, Adv. Synth. Catal., 2011, 353, 749.
105 18 To the best of our knowledge, the only precedent for Cl instead of tht
displacement at Au arises from the reaction of an anionic
dodecaborateꢀsubstituted phosphine with ClAu(tht): V. Lavallo, J. H.
Wright, F. S. Tham, and S. Quinlivan, Angew. Chem. Int. Ed., 2013,
52, 3172.
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Anderson, J. Rittle, and J. C. Peters, Nature, 2013, 501, 84. (e) M. P. 100
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Bouhadir, J. C. Barthelat, S. SaboꢀEtienne, and D. Bourissou, Dalton
Trans., 2007, 2370. (b) O. Tutusaus, C. Ni, and N. K. Szymczak, J.
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(a) P. Gualco, T. P. Lin, M. Sircoglou, M. Mercy, S. Ladeira, G.
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Bourissou, Angew. Chem. Int. Ed., 2009, 48, 9892. (b) P. Gualco, M.
Mercy, S. Ladeira, Y. Coppel, L. Maron, A. Amgoune, and D.
4
5
Bourissou, Chem. Eur. J., 2010, 16, 10808. (c) T. P. Lin, I. S. Ke, 110 19 The
hydrolysis
product
2 2
[((Mes P(C=CHPh)Al(Cl)(tBu ))Au
and F. P. Gabbaï, Angew. Chem. Int. Ed., 2012, 51, 4985. (d) C.
Tschersich, C. Limberg, S. Roggan, C. Herwig, N. Ernsting, S.
Kovalenko, and S. Mebs, Angew. Chem. Int. Ed., 2012, 51, 4989. (e)
I. S. Ke and F. P. Gabbaï, Inorg. Chem., 2013, 52, 7145. (f) I. S. Ke,
J. S. Jones, and F. P. Gabbaï, Angew. Chem. Int. Ed., 2014, 53, 2633.
(a) F. G. Fontaine and D. Zargarian, J. Am. Chem. Soc., 2004, 126,
(Mes P(HC=CHPh))] has been identified by NMR and MS. Cleavage
2
of the Al–vinyl rather than Al–Cl bond probably results from the
preferential attack of water on the threeꢀcoordinate Al center for both
steric and electronic reasons.
2 2
115 20 For bridged R(tBu) Al–Cl–AlR(tBu) species, see: (a) W. Uhl, D.
6
Heller, M. Rohling, and J. Kösters, Inorg. Chim. Acta., 2011, 374,
359; (b) W. Uhl, D. Heller, J. Kösters, E.ꢀU. Würthwein, and N.
Ghavtadze, Eur. J. Inorg. Chem., 2012, 1359.
8
786. (b) M. H. Thibault, J. Boudreau, S. Mathiotte, F. Drouin, O.
Sigouin, A. Michaud, and F. G. Fontaine, Organometallics, 2007, 26,
3
5
807. (c) J. Boudreau and F. G. Fontaine, Organometallics, 2011, 30,
11.
21 see Supporting Information.
120 22 (a) J. P. Weyrauch, A. S. K. Hashmi, A. Schuster, T. Hengst, S.
Schetter, A. Littmann, M. Rudolph, M. Hamzic, J. Visus, F.
Rominger, W. Frey, and J. W. Bats Chem. Eur. J., 2010, 16, 956. (b)
M. M. Hansmann, F. Rominger, M. P. Boone, D. W. Stephan, and A.
S. K. Hashmi, Organometallics, 2014, 33, 4461. (c) W. Wang, M.
Kumar, G. B. Hammond, and B. Xu, Org. Lett., 2014, 16, 636.
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(a) M. Sircoglou, G. Bouhadir, N. Saffon, K. Miqueu, and D.
Bourissou, Organometallics, 2008, 27, 1675. (b) M. Sircoglou, N.
Saffon, K. Miqueu, G. Bouhadir and D. Bourissou, Organometallics,
2
013, 32, 6780.
(a) M. Sircoglou, M. Mercy, N. Saffon, Y. Coppel, G. Bouhadir, L. 125
Maron, and D. Bourissou, Angew. Chem. Int. Ed., 2009, 48, 3454. (b)
E. J. Derrah, M. Sircoglou, M. Mercy, S. Ladeira, G. Bouhadir, K.
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6
57.
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M. A. Courtemanche, J. Larouche, M. A. Légaré, W. Bi, L. Maron,
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Slootweg, K. Lammertsma, and W. Uhl, Angew. Chem. Int. Ed.,
0
2
011, 50, 3925. (b) C. Appelt, J. C. Slootweg, K. Lammertsma, and
W. Uhl, Angew. Chem. Int. Ed., 2012, 51, 5911. (c) C. Appelt, J. C.
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2
3
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033.
11 For the reactivity of (R
9
2
2 2 2
PCH AlMe ) (R = Me, tBu) with small
organic molecules, see: (a) J. Boudreau, M. A. Courtemanche, and F.
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