Organometallics
Article
(30) The alkyne-tethered phosphine ligand diphenyl(4-(triisopro-
pylsilyl)but-3-yn-1-yl)phosphane coordinates to two distinct gold
centers, producing an A-frame type complex. The alkene-tethered
phosphine ligand (4-methylpent-3-en-1-yl)diphenylphosphane also
coordinates to two distinct gold centeres, producing linkage polymers.
(31) Brown, T. J.; Sugie, A.; Dickens, M. G.; Widenhoefer, R. A.
Organometallics 2010, 29, 4207−4209.
(59) Gasperini, D.; Collado, A.; Gomez
́
-Suar
́
ez, A.; Cordes, D. B.;
Slawin, A. M. Z.; Nolan, S. P. Chem. - Eur. J. 2015, 21, 5403−5412.
(60) Kumar, M.; Jasinski, J.; Hammond, G. B.; Xu, B. Chem. - Eur. J.
2014, 20, 3113−3119.
(62) Amster, R. L.; Taylor, R. C. Spectrochim. Acta 1964, 20, 1487−
1502.
−
(32) PR3 = (2-biphenyl)di-tert-butylphosphine, allene = 3-methyl-
buta-1,2-diene.
(63) Hydrolysis of BF4 anions to afford HOBF3 units is known. In
order to rule out the formation of this species, further analyses were
(64) Bondi, A. J. Phys. Chem. 1964, 68, 441−451.
(65) No additonal splitting of signals was detected in non-proton-
decoupled fluorine NMR spectra.
(66) It could be assumed that the more symmetrical environment of
the boron nucleus in the outer coordination sphere would impede the
quadrupole relaxation that enabled the observation of heteronuclear
coupling in the inner-sphere coordinating counterion.
(33) Florke, U.; Hoffmann, A.; Henkel, G. CCDC 1452942:
̈
(34) Herbert, D. E.; Lara, N. C.; Agapie, T. Chem. - Eur. J. 2013, 19,
16453−16460.
(35) Rossin, A.; Tuci, G.; Giambastiani, G.; Peruzzini, M.
ChemPlusChem 2014, 79, 406−412.
(36) Doring, A.; Florke, U.; Hoffmann, A.; Jones, M. D.; Kuckling,
̈
̈
D.; Michaelis de Vasconcellos, J.; Herres-Pawlis, S. Z. Anorg. Allg.
Chem. 2015, 641, 2147−2156.
(67) (a) Herrmann, W. A.; Runte, O.; Artus, G. J. Organomet. Chem.
1995, 501, C1−C4. (b) de Fremont, P.; Singh, R.; Stevens, E. D.;
́
(37) Salem, H.; Milstein, D.; Shimon, L. J. W. CCDC 668208:
Experimental Crystal Structure Determination 2007, DOI: 10.5517/
Petersen, J. L.; Nolan, S. P. Organometallics 2007, 26, 1376−1385.
(c) Tapu, D.; Dixon, D. A.; Roe, C. Chem. Rev. 2009, 109, 3385−3407.
(68) Upfield shifts indicate a lower electron density at the carbenic
carbon atom associated with a higher net charge transfer of the ligand
to the gold atom, as dictated by the electron deficiency of the more
Lewis acidic gold atom.
(38) Maier, J. M.; Li, P.; Hwang, J.; Smith, M. D.; Shimizu, K. D. J.
Am. Chem. Soc. 2015, 137, 8014−8017.
(39) Friedemann, R.; Seppelt, K. Eur. J. Inorg. Chem. 2013, 2013,
1197−1206.
(69) Gaillard, S.; Slawin, A. M. Z.; Bonura, A. T.; Stevens, E. D.;
(40) Chernyshova, E. S.; Goddard, R.; Porschke, K.-R. Organo-
̈
Nolan, S. P. Organometallics 2010, 29, 394−402.
metallics 2007, 26, 3236−3251.
(70) Muller, R. S. R. Homogeneous gold catalysts: development of
̈
(41) Fawcett, J.; Harding, D. A. J.; Hope, E. G.; Singh, K.; Solan, G.
A. Dalton Trans. 2009, 6861.
applications for gold(I) catalysts bearing N-heterocyclic carbene
ligands. University of St Andrews, 2011.
́
(42) Michelet, B.; Colard-Itte, J.-R.; Thiery, G.; Guillot, R.; Bour, C.;
(71) Gom
A.; Cavallo, L.; Nolan, S. P. ACS Catal. 2014, 4, 2701−2705.
(72) Collado, A.; Gomez-Suarez, A.; Martin, A. R.; Slawin, A. M. Z.;
́ ́
ez-Suarez, A.; Gasperini, D.; Vummaleti, S. V. C.; Poater,
Gandon, V. Chem. Commun. 2015, 51, 7401−7404.
(43) Lingnau, R.; Strahle, J. Angew. Chem., Int. Ed. Engl. 1988, 27,
̈
́
́
436−436.
Nolan, S. P. Chem. Commun. 2013, 49, 5541−5543.
(73) Meiries, S.; Nolan, S. Synlett 2014, 25, 393−398.
(44) Abadie, M.-A.; Trivelli, X.; Medina, F.; Capet, F.; Roussel, P.;
Agbossou-Niedercorn, F.; Michon, C. ChemCatChem 2014, 6, 2235−
2239.
́ ́
(74) Brule, E.; Gaillard, S.; Rager, M.-N.; Roisnel, T.; Guerineau, V.;
Nolan, S. P.; Thomas, C. M. Organometallics 2011, 30, 2650−2653.
(45) Tlahuext-Aca, A.; Hopkinson, M. N.; Daniliuc, C. G.; Glorius, F.
Chem. - Eur. J. 2016, 22, 11587−11592.
(75) Formation of 8 would coincide with formation of 1 equiv of
−
HBF4 from deprotonation of water by the second equivalent of BF4
in 3. For dedicated experiments that show a shift of this equilibrium in
(46) Krossing, I.; Raabe, I. Chem. - Eur. J. 2004, 10, 5017−5030.
(47) Mankad, N. P.; Toste, F. D. Chem. Sci. 2012, 3, 72−76.
(48) Wyss, C. M.; Tate, B. K.; Bacsa, J.; Wieliczko, M.; Sadighi, J. P.
Polyhedron 2014, 84, 87−95.
́
the presence of excess HBF4, see: Gaillard, S.; Bosson, J.; Ramon, R. S.;
Nun, P.; Slawin, A. M. Z.; Nolan, S. P. Chem. - Eur. J. 2010, 16,
13729−13740.
(49) Mankad, N. P.; Toste, F. D. J. Am. Chem. Soc. 2010, 132,
12859−12861.
(76) (a) Fu, M.-C.; Shang, R.; Cheng, W.-M.; Fu, Y. ACS Catal.
2016, 6, 2501−2505. (b) Zuccaccia, D.; Belpassi, L.; Tarantelli, F.;
Macchioni, A. J. Am. Chem. Soc. 2009, 131, 3170−3171.
(50) Winston, M. S.; Wolf, W. J.; Toste, F. D. J. Am. Chem. Soc. 2015,
137, 7921−7928.
́ ́
(77) Oonishi, Y.; Gomez-Suarez, A.; Martin, A. R.; Nolan, S. P.
(51) Kumar, R.; Linden, A.; Nevado, C. Angew. Chem., Int. Ed. 2015,
54, 14287−14290.
Angew. Chem., Int. Ed. 2013, 52, 9767−9771.
(78) Frisch, M. J.; Trucks, G. W.; Schlegel, H. B.; Scuseria, G. E.;
Robb, M. A.; Cheeseman, J. R.; Montgomery, J. A., Jr.; Vreven, T.;
Kudin, K. N.; Burant, J. C.; Millam, J. M.; Iyengar, S. S.; Tomasi, J.;
Barone, V.; Mennucci, B.; Cossi, M.; Scalmani, G.; Rega, N.;
Petersson, G. A.; 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, J. E.; Hratchian, H. P.; Cross, J.
B.; Adamo, C.; Jaramillo, J.; Gomperts, R.; Stratmann, R. E.; Yazyev,
O.; Austin, A. J.; Cammi, R.; Pomelli, C.; Ochterski, J. W.; Ayala, P. Y.;
Morokuma, K.; Voth, G. A.; Salvador, P.; Dannenberg, J. J.;
Zakrzewski, V. G.; Dapprich, S.; Daniels, A. D.; Strain, M. C.;
Farkas, O.; Malick, D. K.; Rabuck, A. D.; Raghavachari, K.; Foresman,
J. B.; Ortiz, J. V.; Cui, Q.; Baboul, A. G.; Clifford, S.; Cioslowski, J.;
Stefanov, B. B.; Liu, G.; Liashenko, A.; Piskorz, P.; Komaromi, I.;
Martin, R. L.; Fox, D. J.; Keith, T.; Al-Laham, M. A.; Peng, C. Y.;
Nanayakkara, A.; Challacombe, M.; Gill, P. M. W.; Johnson, B.; Chen,
W.; Wong, M. W.; Gonzalez, C.; Pople, J. A. Gaussian09 Revision B.01;
Gaussian Inc., Wallingford, CT.
(52) Laitar, D. S.; Muller, P.; Gray, T. G.; Sadighi, J. P.
̈
Organometallics 2005, 24, 4503−4505.
(53) Veenboer, R. M. P.; Nolan, S. P. Green Chem. 2015, 17, 3819−
3825.
́ ́
(54) (a) Gomez-Suarez, A.; Oonishi, Y.; Meiries, S.; Nolan, S. P.
Organometallics 2013, 32, 1106−1111. (b) Biannic, B.; Aponick, A.
Eur. J. Org. Chem. 2011, 2011, 6605−6617. (c) Veenboer, R. M. P.;
Dupuy, S.; Nolan, S. P. ACS Catal. 2015, 5, 1330−1334. (d) Dupuy,
S.; Gasperini, D.; Nolan, S. P. ACS Catal. 2015, 5, 6918−6921.
(55) Mohlmann, L.; Wendt, O. F.; Johnson, M. T. Acta Crystallogr.,
̈
Sect. E: Struct. Rep. Online 2011, 67, m719−m720.
́
(56) (a) Marion, N.; Ramon, R. S.; Nolan, S. P. J. Am. Chem. Soc.
2009, 131, 448−449. (b) Marion, N.; Gealageas, R.; Nolan, S. P. Org.
Lett. 2007, 9, 2653−2656.
(57) Such complexes are known to be catalytically inactive, and their
facile formation under these general conditions explains why IMes
ligands are only rarely used in homogeneous catalysis in comparison to
the slightly larger IPr ligand.
(79) (a) Perdew, J. P. Phys. Rev. B: Condens. Matter Mater. Phys. 1986,
33, 8822−8824. (b) Perdew, J. P. Phys. Rev. B: Condens. Matter Mater.
(58) Cordon
metallics 2016, 35, 732−740.
́ ́
, J.; Lopez-de-Luzuriaga, J. M.; Monge, M. Organo-
H
Organometallics XXXX, XXX, XXX−XXX