, Cette fois-ci, la distance Cu-Cu est trop grande pour permettre une liaison intermétallique (2,89 Å)

, Une légère dissymétrie peut être observée entre les ions cuivre, avec Cu1 plus proche des atomes de soufre et d'azote tertiaire du ligand

, Cu1-Cu2, vol.2, p.892

, Cu1-S1, vol.2, p.183

, Cu2-S1, vol.2, p.220

, Cu1-N1, vol.2, p.19

, Cu1-N2, vol.1, issue.11, p.979

, Cu2-N3, vol.2, p.193

, Cu2-N4, vol.2, p.127

, Cu1-N41, vol.2, p.39

. S-cu1, Cu2, vol.49, issue.10, p.48

-. Cu1, , vol.82, p.15

. S-cu2, Cu1, vol.48, issue.8, p.39

. Dir, 95/2/CE DU Parlem, Eur. DU Cons, 1995.

D. J. Wuebbles, Science, vol.326, pp.56-57, 2009.

A. R. Ravishankara, J. S. Daniel, and R. W. Portmann, Science, p.123, 2009.

D. S. Reay, E. A. Davidson, K. A. Smith, P. Smith, J. M. Melillo et al., Nat. Clim. Chang, vol.2, pp.410-416, 2012.

J. Pérez-ram??rezram??rez, F. Kapteijn, K. Schöffel, and J. A. Moulijn, Appl. Catal. B Environ, vol.44, pp.117-151, 2003.

M. H. Thiemens and W. C. Trogler, , pp.932-934, 1991.

A. Colorado, V. Mcdonell, and S. Samuelsen, Int. J. Hydrogen Energy, vol.42, pp.711-719, 2017.

, Emission Database for Global Atmospheric Research EDGAR, Nitrous oxide emissions (thousand metric tons of CO2 equivalent

K. Khalil and M. Bruno, Emissions de N2O par nitrification et dénitrification à l'échelle de la motte de sol: effet de la structure du sol, de l'aération et des activités microbiennes

H. Tian, C. Lu, P. Ciais, A. M. Michalak, J. G. Canadell et al., Nature, vol.531, pp.225-228, 2016.

M. Maze and M. Fujinaga, Best Pract. Res. Clin. Anaesthesiol, vol.15, pp.339-348, 2001.

G. D. Parbrook and . Br, J. Anaesth, vol.40, pp.365-372, 1968.

J. Van-amsterdam, T. Nabben, W. Van-den, and . Brink, Regul. Toxicol. Pharmacol, vol.73, pp.790-796, 2015.

J. Vesna, B. Nicholas, and O. J. Br, J. Pharmacol, vol.130, pp.1692-1698, 2009.

J. Weimann, Best Pract. Res. Clin. Anaesthesiol, vol.17, pp.47-61, 2003.

D. Rosemary, L. Michael, P. Janet, C. Israel, M. Barbara et al., Eur. J. Biochem, vol.104, pp.419-422, 2005.

C. L. Winek, W. W. Wahba, and L. Rozin, Forensic Sci. Int, vol.73, pp.139-141, 1995.

M. L. Hays and T. P. Hanusa, Tetrahedron Lett, vol.36, pp.2435-2436, 1995.

A. G. Tskhovrebov, E. Solari, R. Scopelliti, and K. Severin, Organometallics, vol.33, pp.2405-2408, 2014.

A. J. Arduengo and G. Bertrand, Chem. Rev, vol.109, pp.3209-3210, 2009.

A. J. Arduengo, R. L. Harlow, and M. Kline, J. Am. Chem. Soc, vol.113, pp.361-363, 1991.

D. Bourissou, O. Guerret, F. P. Gabbaï, and G. Bertrand, Chem. Rev, vol.100, pp.39-92, 2000.

M. Poyatos, J. A. Mata, and E. Peris, Chem. Rev, vol.109, pp.3677-3707, 2009.

O. Schuster, L. Yang, H. G. Raubenheimer, and M. Albrecht, Chem. Rev, vol.109, pp.3445-3478, 2009.

P. De-frémont, N. Marion, and S. P. Nolan, Coord. Chem. Rev, vol.253, pp.862-892, 2009.

K. Hirai, T. Itoh, and H. Tomioka, Chem. Rev, vol.109, pp.3275-3332, 2009.

J. Vignolle, X. Cattoën, and D. Bourissou, Chem. Rev, vol.109, pp.3333-3384, 2009.

A. G. Tskhovrebov, E. Solari, R. Scopelliti, and K. Severin, Inorg. Chem, vol.52, pp.11688-11690, 2013.

A. G. Tskhovrebov, E. Solari, M. D. Wodrich, R. Scopelliti, and K. Severin, J. Am. Chem. Soc, vol.134, pp.1471-1473, 2012.

T. A. , N. L. , S. Euro, S. Rosario, and S. Kay, Angew. Chem. Int. Ed, vol.54, pp.1289-1292, 2014.

L. Y. Eymann, R. Scopelliti, F. F. Tirani, K. Severin, and C. Eur, J, vol.24, pp.7957-7963, 2018.

N. Tokitoh, H. Suzuki, R. Okazaki, and K. Ogawa, J. Am. Chem. Soc, vol.115, pp.10428-10429, 1993.

M. Kira, Proc. Japan Acad. Ser. B, vol.88, pp.167-191, 2012.

P. D. Magnus, J. Am. Chem. Soc, p.1762, 1999.

H. B. Yokelson, A. J. Millevolte, G. R. Gillette, and R. West, J. Am. Chem. Soc, vol.109, pp.6865-6866, 1987.

R. West, M. J. Fink, and J. Michl, , vol.214, pp.1343-1344, 1981.

N. Tokitoh, H. Suzuki, R. Okazaki, and K. Ogawa, J. Am. Chem. Soc, vol.115, pp.10428-10429, 1993.

S. Khan, R. Michel, D. Koley, H. W. Roesky, and D. Stalke, Inorg. Chem, vol.50, pp.10878-10883, 2011.

W. Nils, N. Wolfgang, P. Kurt, M. Peter, and C. Eur, J, vol.8, pp.2730-2739, 2002.

R. Azhakar, K. Pröpper, B. Dittrich, and H. W. Roesky, Organometallics, vol.31, pp.7586-7590, 2012.

Z. Mo, T. Szilvási, Y. Zhou, S. Yao, and M. Driess, Angew. Chem. Int. Ed, vol.56, pp.3699-3702, 2017.

R. Zeng, M. Feller, Y. Ben-david, and D. Milstein, J. Am. Chem. Soc, vol.139, pp.5720-5723, 2017.

G. C. Welch, R. R. Juan, J. D. Masuda, and D. W. Stephan, Science, vol.314, pp.1124-1126, 2006.

D. W. Stephan, J. Am. Chem. Soc, vol.137, pp.10018-10032, 2015.

D. W. Stephan, Acc. Chem. Res, vol.48, pp.306-316, 2015.

E. Otten, R. C. Neu, and D. W. Stephan, J. Am. Chem. Soc, vol.131, pp.9918-9919, 2009.

G. Ménard, J. A. Hatnean, H. J. Cowley, A. J. Lough, J. M. Rawson et al., J. Am. Chem. Soc, vol.135, pp.6446-6449, 2013.

E. Theuergarten, T. Bannenberg, M. D. Walter, D. Holschumacher, M. Freytag et al., Dalt. Trans, vol.43, pp.1651-1662, 2014.

A. Berkefeld, W. E. Piers, and M. Parvez, J. Am. Chem. Soc, vol.132, pp.10660-10661, 2010.

Y. Li and J. N. Armor, Appl. Catal. B Environ, vol.1, pp.21-29, 1992.

A. Zecchina, M. Rivallan, G. Berlier, C. Lamberti, and G. Ricchiardi, Phys. Chem. Chem. Phys, vol.9, pp.3483-3499, 2007.

T. Kunihiko, Y. Takashi, K. Takao, and T. Juntaro, Org. Synth, p.48, 1989.

F. Labtech and . Reactors,

J. A. Luque-urrutia and A. Poater, Inorg. Chem, vol.56, pp.14383-14387, 2017.

R. Zeng, M. Feller, Y. Diskin-posner, L. J. Shimon, Y. Ben-david et al., J. Am. Chem. Soc, vol.140, pp.7061-7064, 2018.

G. I. Panov, CATTECH, vol.4, pp.18-31, 2000.

M. Parfenov, E. Starokon, L. Pirutko, and G. I. Panov, J. Catal, vol.318, pp.14-21, 2014.

D. J. Xiao, E. D. Bloch, J. A. Mason, W. L. Queen, M. R. Hudson et al., Nat. Chem, vol.6, pp.590-595, 2014.

A. N. Chernysheva, E. K. Beloglazkina, A. A. Moiseeva, R. L. Antipin, N. Zyk et al., Mendeleev Commun, vol.22, pp.70-72, 2012.

A. Yamamoto, S. Kitazume, L. S. Pu, and S. Ikeda, J. Am. Chem. Soc, vol.93, pp.371-380, 1971.

T. L. Gianetti, R. E. Rodríguez-lugo, J. R. Harmer, M. Trincado, M. Vogt et al., Angew. Chem. Int. Ed, vol.55, pp.15323-15328, 2016.

U. Jayarathne, S. R. Parmelee, and N. P. Mankad, Inorg. Chem, vol.53, pp.7730-7737, 2014.

T. Yamada, K. Hashimoto, Y. Kitaichi, K. Suzuki, and T. Ikeno, Chem. Lett, vol.30, pp.268-269, 2001.

T. Corona and A. Company, Dalt. Trans, vol.45, pp.14530-14533, 2016.

Y. B. , R. J. , Z. P. , and S. L. , Angew. Chem. Int. Ed, vol.50, pp.12342-12346, 2011.

C. Li, K. Sun, and C. Cheng, J. Chem. Soc. Dalt. Trans, pp.1025-1029, 1992.

K. Gregor, J. Loïc, and S. Kay, Angew. Chem. Int. Ed, vol.52, pp.6302-6305, 2013.

S. Saito, H. Ohtake, N. Umezawa, Y. Kobayashi, N. Kato et al., Chem. Comm, vol.49, pp.8979-8981, 2013.

A. J. Timmons and M. D. Symes, Chem. Soc. Rev, vol.44, pp.6708-6722, 2015.

K. Brown, M. Tegoni, M. Prudêncio, A. S. Pereira, S. Besson et al., Nat. Struct. Biol, 2000.

K. Brown, K. Djinovic-carugo, T. Haltia, I. Cabrito, M. Saraste et al., J. Biol. Chem, vol.275, pp.41133-41136, 2000.

S. Larsson, B. Källebring, P. Wittung, and B. G. Malmström, Proc. Natl. Acad. Sci, vol.92, pp.7167-7171, 1995.

A. Pomowski, W. G. Zumft, P. M. Kroneck, and O. Einsle, Nature, vol.477, pp.234-237, 2011.

E. M. Johnston, C. Carreira, S. Dell'acqua, S. G. Dey, S. R. Pauleta et al., J. Am. Chem. Soc, vol.139, pp.4462-4476, 2017.

N. A. Piro, M. F. Lichterman, W. H. Harman, and C. J. Chang, J. Am. Chem. Soc, vol.133, pp.2108-2111, 2011.

J. N. Armor and H. Taube, J. Am. Chem. Soc, vol.91, pp.6874-6876, 1969.

V. W. , -. Yam, W. Lee, and T. Lai, J. Chem. Soc. Chem. Commun, pp.1571-1573, 1993.

B. J. Johnson, W. E. Antholine, S. Lindeman, M. J. Graham, and N. P. Mankad, J. Am. Chem. Soc, vol.138, pp.13107-13110, 2016.

B. J. Johnson, W. E. Antholine, S. Lindeman, and N. P. Mankad, Chem. Comm, vol.51, pp.11860-11863, 2015.

I. Bar-nahum, A. K. Gupta, S. M. Huber, M. Z. Ertem, C. J. Cramer et al., J. Am. Chem. Soc, vol.131, pp.2812-2814, 2009.

S. Bagherzadeh and N. P. Mankad, Chem. Comm, vol.54, pp.1097-1100, 2018.

S. Torelli, M. Orio, J. Pécaut, H. Jamet, L. L. Pape et al., Angew. Chem. Int. Ed, vol.49, pp.8249-8252, 2010.

C. Esmieu, M. Orio, S. Torelli, L. L. Pape, J. Pecaut et al., Chem. Sci, vol.5, pp.4774-4784, 2014.

F. Gennarini, R. David, I. López, Y. L. Mest, M. Réglier et al., Inorg. Chem, vol.56, pp.7707-7719, 2017.

F. Gennarini, A. Kochem, J. Isaac, A. Mansour, I. López et al., Inorg. Chim. Acta, vol.481, pp.113-119, 2018.

N. Berthet, V. Martel-frachet, F. Michel, C. Philouze, S. Hamman et al., Dalt. Trans, vol.42, pp.8468-8483, 2013.

C. E. Elwell, N. L. Gagnon, B. D. Neisen, D. Dhar, A. D. Spaeth et al., Chem. Rev, vol.117, pp.2059-2107, 2017.

X. Huang and J. T. Groves, Chem. Rev, vol.118, pp.2491-2553, 2018.

J. M. Campos-martin, G. Blanco-brieva, and J. L. Fierro, Angew. Chem. Int. Ed, vol.45, pp.6962-6984, 2006.

V. Russo, R. Tesser, E. Santacesaria, and M. D. Serio, Ind. Eng. Chem. Res, vol.52, pp.1168-1178, 2013.

A. A. Gewirth, J. A. Varnell, and A. M. Diascro, Chem. Rev, vol.118, pp.2313-2339, 2018.

M. L. Pegis, C. F. Wise, D. J. Martin, and J. M. Mayer, Chem. Rev, vol.118, pp.2340-2391, 2018.

K. Ray, F. F. Pfaff, B. Wang, and W. Nam, J. Am. Chem. Soc, vol.136, pp.13942-13958, 2014.

L. Que and W. B. Tolman, Nature, vol.455, pp.333-340, 2008.

D. A. Quist, D. E. Diaz, J. J. Liu, and K. D. Karlin, JBIC J. Biol. Inorg. Chem, vol.22, pp.253-288, 2017.

G. Fermi, M. F. Perutz, and R. G. Shulman, Proc. Natl. Acad. Sci, vol.84, pp.6167-6168, 1987.

V. C. Wang, S. Maji, P. P. Chen, H. K. Lee, S. S. Yu et al., Chem. Rev, vol.117, pp.8574-8621, 2017.

S. Ferguson-miller and G. T. Babcock, Chem. Rev, vol.96, pp.2889-2908, 1996.

S. Hirota, T. Kawahara, M. Beltramini, P. D. Muro, R. S. Magliozzo et al., J. Biol. Chem, vol.283, pp.31941-31948, 2008.

M. M. Whittaker and J. W. Whittaker, J. Biol. Chem, vol.263, pp.6074-6080, 1988.

E. I. Solomon, D. E. Heppner, E. M. Johnston, J. W. Ginsbach, J. Cirera et al., Chem. Rev, vol.114, pp.3659-3853, 2014.

I. G. Denisov, T. M. Makris, S. G. Sligar, and I. Schlichting, Chem. Rev, vol.105, pp.2253-2278, 2005.

P. R. Ortiz-de-montellano, Chem. Rev, vol.110, pp.932-948, 2010.

Z. Sun, B. Fridrich, A. Santi, S. Elangovan, and K. Barta, Chem. Rev, vol.118, pp.614-678, 2018.

H. Komori and Y. Higuchi, J. Biochem, vol.158, pp.293-298, 2015.

E. I. Solomon, A. J. Augustine, and J. Yoon, Dalt. Trans, pp.3921-3932, 2008.

N. Mano and A. De-poulpiquet, Chem. Rev, vol.118, pp.2392-2468, 2018.

N. G. Connelly and W. E. Geiger, Chem. Rev, vol.96, pp.877-910, 1996.

I. Noviandri, K. N. Brown, D. S. Fleming, P. T. Gulyas, P. A. Lay et al., J. Phys. Chem. B, vol.103, pp.6713-6722, 1999.

M. Roemer, B. W. Skelton, M. J. Piggott, and G. A. Koutsantonis, Dalt. Trans, vol.45, pp.18817-18821, 2016.

L. Shaoyung, Kinetic study of the reaction of ferrocenes and ferrocenium ions with ground and excited states of tris(2,2-bipyridine)chromium ions and the preparation and homolysis of organocobalt complexes

D. Gao, Q. Gu, C. Zheng, and S. You, Acc. Chem. Res, vol.50, pp.351-365, 2017.

K. Mase, K. Ohkubo, and S. Fukuzumi, J. Am. Chem. Soc, vol.135, pp.2800-2808, 2013.

R. Cao, C. Saracini, J. W. Ginsbach, M. T. Kieber-emmons, M. A. Siegler et al., J. Am. Chem. Soc, vol.138, pp.7055-7066, 2016.

M. Gennari, D. Brazzolotto, J. Pécaut, M. Cherrier, C. J. Pollock et al., J. Am. Chem. Soc, vol.137, pp.8644-8653, 2015.

S. Fukuzumi, H. Kotani, H. R. Lucas, K. Doi, T. Suenobu et al., J. Am. Chem. Soc, vol.132, pp.6874-6875, 2010.

D. Das, Y. Lee, K. Ohkubo, W. Nam, K. D. Karlin et al., J. Am. Chem. Soc, vol.135, pp.2825-2834, 2013.

S. Kakuda, R. L. Peterson, K. Ohkubo, K. D. Karlin, and S. Fukuzumi, J. Am. Chem. Soc, vol.135, pp.6513-6522, 2013.

L. Tahsini, H. Kotani, Y. Lee, J. Cho, W. Nam et al., Chem. -A Eur. J, vol.18, pp.1084-1093, 2012.

S. Fukuzumi, L. Tahsini, Y. Lee, K. Ohkubo, W. Nam et al., J. Am. Chem. Soc, vol.134, pp.7025-7035, 2012.

J. Jung, S. Liu, K. Ohkubo, M. M. Abu-omar, and S. Fukuzumi, Inorg. Chem, vol.54, pp.4285-4291, 2015.

Y. Wang, M. L. Pegis, J. M. Mayer, and S. S. Stahl, J. Am. Chem. Soc, vol.139, pp.16458-16461, 2017.

S. Fukuzumi, S. Mandal, K. Mase, K. Ohkubo, H. Park et al., J. Am. Chem. Soc, vol.134, pp.9906-9909, 2012.

Z. Halime, H. Kotani, Y. Li, S. Fukuzumi, and K. D. Karlin, Proc. Natl. Acad. Sci, vol.108, pp.13990-13994, 2011.

S. Brooker, Coord. Chem. Rev, vol.222, pp.33-56, 2001.

W. Huang, G. Masuda, S. Maeda, H. Tanaka, T. Hino et al., Inorg. Chem, vol.47, pp.468-480, 2008.

K. Nishide, T. Miyamoto, K. Kumar, S. Ohsugi, and M. Node, Tetrahedron Lett, vol.43, pp.8569-8573, 2002.

Y. Yoshida, D. Barrett, H. Azami, C. Morinaga, S. Matsumoto et al., Bioorg. Med. Chem, vol.7, pp.2647-2666, 1999.

Y. Chen, Q. Zhang, B. Zhang, P. Xia, Y. Xia et al., Bioorg. Med. Chem, vol.12, pp.6383-6387, 2004.

C. N. Njiojob, E. A. Owens, L. Narayana, H. Hyun, H. S. Choi et al., J. Med. Chem, vol.58, pp.2845-2854, 2015.

V. Novakova, M. Miletin, T. Filandrová, J. Len?o, A. R??i?ka et al., J. Org. Chem, vol.79, pp.2082-2093, 2014.

A. Mondragón, M. Flores-alamo, P. R. Martínez-alanis, G. Aullón, V. M. Ugalde-saldívar et al., Inorg. Chem, vol.54, pp.619-627, 2015.

J. P. Gilday, P. Lenden, J. D. Moseley, and B. G. Cox, J. Org. Chem, vol.73, pp.3130-3134, 2008.

S. Kimura, E. Bill, E. Bothe, T. Weyhermüller, and K. Wieghardt, J. Am. Chem. Soc, vol.123, pp.6025-6039, 2001.

J. Clayden and J. Senior, , pp.2769-2772, 2009.

A. W. Addison, T. N. Rao, J. Reedijk, J. Van-rijn, and G. C. Verschoor, J. Chem. Soc. Dalt. Trans, pp.1349-1356, 1984.

J. L. Que, Physical Methods in Bioinorganic Chemistry, 2000.

N. Elgrishi, K. J. Rountree, B. D. Mccarthy, E. S. Rountree, T. T. Eisenhart et al., J. Chem. Educ

R. R. Gagne, C. A. Koval, T. J. Smith, and M. C. Cimolino, J. Am. Chem. Soc, vol.101, pp.4571-4580, 1979.

C. Esmieu, M. Orio, J. Mangue, J. Pécaut, S. Ménage et al., Chem. -A Eur. J, vol.24, pp.5060-5063, 2018.

D. D. Lecloux, R. Davydov, and S. J. Lippard, J. Am. Chem. Soc, vol.120, pp.6810-6811, 1998.

R. Gupta, Z. H. Zhang, D. Powell, M. P. Hendrich, and A. S. Borovik, Inorg. Chem, vol.41, pp.5100-5106, 2002.

J. R. Hagadorn, T. I. Zahn, J. L. Que, and W. B. Tolman, Dalt. Trans, pp.1790-1794, 2003.

J. Kuzelka, S. Mukhopadhyay, B. Spingler, and S. J. Lippard, Inorg. Chem, vol.43, pp.1751-1761, 2004.

C. Harding, V. Mckee, and J. Nelson, J. Am. Chem. Soc, vol.113, pp.9684-9685, 1991.

D. D. Lecloux, R. Davydov, and S. J. Lippard, Inorg. Chem, vol.37, pp.6814-6826, 1998.

M. B. Robin and P. Day, Advances in Inorganic Chemistry and Radiochemistry, vol.10, pp.247-422, 1968.

N. Hush, , p.391, 2007.

C. Zonta, O. De-lucchi, R. Volpicelli, and L. Cotarca, Sulfur-Mediated Rearrangements II, pp.131-161, 2007.

H. Kwart and E. R. Evans, J. Org. Chem, vol.31, pp.410-413, 1966.

M. S. Newman and H. A. Karnes, J. Org. Chem, vol.31, pp.3980-3984, 1966.

G. C. Lloyd-jones, J. D. Moseley, and J. S. Renny, Synthesis (Stuttg), pp.661-689, 2008.

M. Burns, G. C. Lloyd-jones, J. D. Moseley, and J. S. Renny, J. Org. Chem, vol.75, pp.6347-6353, 2010.

H. , J. N. , J. Jesús, L. Guy, C. D. Jonathan et al., Angew. Chem. Int. Ed, vol.48, pp.7612-7615, 2009.

S. Brooker, G. B. Caygill, P. D. Croucher, T. C. Davidson, D. L. Clive et al., J. Chem. Soc.{,} Dalt. Trans, pp.3113-3121, 2000.

A. J. Perkowski, C. L. Cruz, and D. A. Nicewicz, J. Am. Chem. Soc, vol.137, pp.15684-15687, 2015.

J. Mangue, Q. Dubreucq, J. Pécaut, S. Ménage, S. Torelli et al., , vol.1, pp.6345-6348, 2016.

S. Jovanovic, K. Kónya, and J. C. Scaiano, Can. J. Chem, vol.73, pp.1803-1810, 1995.

C. Esmieu, M. Orio, L. L. Pape, C. Lebrun, J. Pécaut et al., Inorg. Chem, vol.55, pp.6208-6217, 2016.

K. Takamura, C. Matsubara, and T. Matsumoto, Anal. Sci, vol.24, pp.401-404, 2008.

C. Matsubara, N. Kawamoto, and K. Takamura, Analyst, vol.117, pp.1781-1784, 1992.

G. De-leener, D. Over, C. Smet, D. Cornut, A. G. Porras-gutierrez et al., Inorg. Chem, vol.56, pp.10971-10983, 2017.

W. Iali, P. Lanoe, S. Torelli, D. Jouvenot, F. Loiseau et al., Angew. Chem. Int. Ed, vol.54, pp.8415-8419, 2015.

S. Stoll and A. Schweiger, J. Magn. Reson, vol.178, pp.42-55, 2006.

N. Frank and W. Interdiscip, Rev. Comput. Mol. Sci, vol.2, pp.73-78, 2011.

A. D. Becke, J. Chem. Phys, vol.98, pp.5648-5652, 1993.

C. Lee, W. Yang, and R. G. Parr, Phys. Rev. B, vol.37, pp.785-789, 1988.

A. Schäfer, C. Huber, and R. Ahlrichs, J. Chem. Phys, vol.100, pp.5829-5835, 1994.

F. Neese, J. Comput. Chem, vol.24, pp.1740-1747, 2003.

F. Weigend, Phys. Chem. Chem. Phys, vol.8, pp.1057-1065, 2006.

A. Klamt and G. Schuurmann, J. Chem. Soc. Perkin Trans. 2, pp.799-805, 1993.

R. E. Stratmann, G. E. Scuseria, and M. J. Frisch, J. Chem. Phys, vol.109, pp.8218-8224, 1998.

R. Bauernschmitt and R. Ahlrichs, Chem. Phys. Lett, vol.256, pp.454-464, 1996.

S. Hirata and M. Head-gordon, Chem. Phys. Lett, vol.314, pp.291-299, 1999.

S. Hirata and M. Head-gordon, Chem. Phys. Lett, vol.302, pp.375-382, 1999.

F. Neese, J. Chem. Phys, vol.115, pp.11080-11096, 2001.

D. A. Pantazis, X. Chen, C. R. Landis, and F. Neese, J. Chem. Theory Comput, vol.4, pp.908-919, 2008.

D. A. Pantazis and F. Neese, J. Chem. Theory Comput, vol.5, pp.2229-2238, 2009.

H. Ohmori, T. Takanami, H. Shimada, and M. Masui, Characterization in CH3CN: UV-Vis-NIR (? (nm), ? (M -1 .cm -1, vol.35, p.530, 1987.

, Characterization in acetone : UV-Vis-NIR (? (nm), ? (M -1 .cm -1, p.580

, Characterization in CH3CN: UV-Vis-NIR (? (nm), ? (M -1 .cm -1, p.600

, Characterization in acetone

, UV-Vis-NIR (? (nm), ? (M -1 .cm -1, vol.555, p.435, 1040.

, Characterization in CH3CN: UV-Vis-NIR (? (nm), ? (M -1 .cm -1, vol.790, p.660, 1220.

, Complex (E): Characterization in acetone

, UV-Vis-NIR (? (nm), ? (M -1 .cm -1, vol.560, p.3, 1025.

, UV-Vis-NIR (? (nm), ? (M -1 .cm -1 )): 910 (30), vol.775, p.595

, Complex (F): Characterization in acetone

, UV-Vis-NIR (? nm, ? (M -1, vol.800, p.525

, Characterization in, vol.3

, UV-Vis-NIR (? nm, ? (M -1 .cm -1 )): 1300 (240), p.575

, Note: for low temperature experiment, the mixture of Me8Fc and LutHBF4 was allowed to cool at the CIRE team, p.140

, The TiOTPyP-H reagent (~4.5.10 -5 M) was prepared by dissolving 3.44 mg of commercial TiOTPyP complex (?90%, from TCI) in 100 mL of 0.05 M HCl and stored at 0°C. An aliquot, p.15

, The method was calibrated by replicating the same procedure using aqueous solutions of H2O2 (in the 0-5 µM range, prepared by dilution of a 0.105 M standard solution), instead of the sample solutions. The obtained ?A values (?Acal(i)) were plotted against H2O2 concentration in the final sample, the catalytic solution was added to a mixture of TiOTPyP-H (250 µL), perchloric acid (4.8M, 250 µL) and water (235 µL)

, Asample(i)) was determined. The concentration of H2O2 in the original samples (i.e. before addition to the TiOTPyP reagent solution) is determined by taking into account the dilution factor

, Note 1: 70 % of H2O2 would mean that we also produce 30 % of H2O (yield calculated against the electron quantity in solution)

, Note 2: As TiOTPyP-H reacts with Me8Fc, the titration cannot be done if all the sacrificial reducing agent is not completely consumed. 14. Verify that the pressure in the device didn't change while filling the UV cell with a solution

, Ending an experiment: 1. Stop the motor device

, Open V2 slowly to empty the device until -0.2 bars. 3. Unscrew V1

, Disconnect the needles from the UV cell

, Stop the vacuum pump

, It is further oxidized into its disulfide analog to be easier to handle and subjected to chlorination and nucleophilic substitution with the desired secondary amine to give the targeted ligands. We then envisaged to prepare dissymmetrical units (achieved through routes (A) and (B), Scheme 1) and investigated route (A) that involves the mono-reduction of the O-(2,6-diformyl-4-methylphenyl) dimethylthiocarbamate synthon (1). NaBH 4 was used as typical reducing agent of the aldehyde function

J. Mangue, Q. Dubreucq, .. S. Dr, and . Mønage, CNRS UMR 5249, CEA, 17 rue des martyrs, F-38054, Univ. Grenoble Alpes

. J. Dr, C. Pøcaut, . Inac, and U. Lcib-(umràe-3-cea, Grenoble Alpes), 17 rue des Martyrs, F-38054 Grenoble Cedex 9

L. Bpa)sàs and . Me, MAM)SÀS and targeted dissymmetrical ligands. (a) DABCO, ClCSN(Me) 2 , DMF, 12 h; (b) BF 3 -Et 2 O, (ClCH 2 ) 2 , reflux, Figure 1. Conversion of (1) into (1 a) and formation of (1 b) via tandem reduction /migration of the thiocarbamate moiety

, ChemistrySelect, vol.1, pp.6345-6348, 2016.

-. Wiley, &. Gmbh, . Co, and . Kgaa,

E. I. Solomon, D. E. Heppner, E. M. Johnston, J. W. Ginsbach, J. Cirera et al., Chem. Rev, vol.114, pp.3659-3853, 2014.

C. Esmieu, M. Orio, S. Torelli, L. L. Pape, J. Pecaut et al., Angew. Chem. Int. Ed, vol.5, pp.8249-8252, 2010.

). G. Lloyd-jones, J. D. Moseley, J. S. Renny, ;. M. Burns, G. C. Lloyd-jones et al., Synthesis-Stuttgart, vol.75, pp.131-161, 2007.

). S. Brooker, P. D. Croucher, F. M. Roxburgh, J. Chem, D. Soc et al., Eur. J. Org. Chem, vol.69, pp.619-627, 1996.

). J. Moseley, P. P. Lenden-;-b)-j, P. Gilday, J. D. Lenden, B. G. Moseley et al., J. Org. Chem, vol.63, pp.3130-3134, 2007.

J. N. Harvey, J. Jover, G. C. Lloyd-jones, J. D. Moseley, P. Murray et al., Angew. Chem. Int. Ed, vol.48, pp.7612-7615, 2009.

). S. Brooker, G. B. Caygill, P. D. Croucher, T. C. Davidson, D. L. Clive et al., Coord. Chem. Rev, vol.222, pp.33-56, 2000.

A. J. Perkowski, C. L. Cruz, and D. A. Nicewicz, J. Am. Chem. Soc, vol.137, pp.15684-15687, 2015.

). W. Huang, G. Masuda, S. Maeda, H. Tanaka, T. Hino et al., Inorg. Chem, vol.47, pp.468-480, 2008.

M. Ohsugi, T. Node, D. Lett-;-c)-y.-yoshida, H. Barrett, C. Azami et al., Biorg. Med. Chem, vol.43, p.5136, 1996.

M. Ono, H. Kawashima, A. Nonaka, T. Kawai, M. Haratake et al.,

H. F. Kung, H. Kung, M. Saji, and . Nakayama, J. Med. Chem, vol.49, pp.2725-2730, 2006.

A. Arnoldi, A. Bassoli, L. Merlini, and E. Ragg, J. Chem. Soc., Perkin Trans. 1, pp.1359-1366, 1993.

, Full Papers 6348 ChemistrySelect, vol.1, pp.6345-6348, 2016.

-. Wiley, &. Gmbh, . Co, and . Kgaa,

C. Dr, J. Esmieu, D. S. Mangue, . Ménage, S. Dr et al.,

M. Dr, Orio Institut des Sciences Moléculaires de Marseille, 13097.

J. Dr, . Pécaut-univ.-grenoble-alpes, C. Cea, and . Inac-symmes, , vol.38000

F. Grenoble and . Keywords, Bioinorganic chemistry ? Cu/S assemblies ? mixed valence ? spectroscopy ?

G. Blondin and J. J. Girerd, Chem. Rev, vol.90, pp.1359-1376, 1990.

N. Prassides, ). W. Adv-sci-i-c-mat-;-c, W. Kaim, J. Bruns, V. Poppe et al., J. Mol. Struct, vol.343, pp.221-228, 1991.

E. I. Solomon, T. C. Brunold, M. I. Davis, J. N. Kemsley, S. K. Lee et al., Angew. Chem. Int. Ed, vol.100, pp.3659-3853, 2000.

M. D. Ward, Astruc, Acc. Chem. Res, vol.24, pp.842-851, 1995.

R. P. Houser, V. G. Young, and W. B. Tolman, Angew. Chem. Int. Ed, vol.118, pp.5662-5666, 1996.

K. Brown, K. Djinovic-carugo, T. Haltia, I. Cabrito, M. Saraste et al., Acta Crystallographica Section F, vol.275, pp.1541-1543, 2000.

A. Pomowski, W. G. Zumft, P. M. Kroneck, and O. Einsle, Nature, vol.477, pp.234-237, 2011.

M. Robin and D. Peter, Adv. Inorg. Chem. Radiochem, vol.10, pp.5-14, 1967.

S. Torelli, M. Orio, J. Pécaut, H. Jamet, L. L. Pape et al., Angew. Chem. Int. Ed, vol.49, pp.4774-4784, 2010.

J. Kuzelka, S. Mukhopadhyay, B. Spingler, S. J. Lippard-;-b)-j, T. I. Hagadorn et al., J. Am. Chem. Soc, vol.43, pp.6810-6811, 1998.

D. D. Lecloux, R. Davydov, and S. J. Lippard, Inorg. Chem, vol.37, pp.6814-6826, 1998.

, Accepted Manuscript Chemistry -A European Journal This article is protected by copyright. All rights reserved

G. Blondin, J. J. Girerd-;-b)k.-prassides, N. Adv-sci-i-cmat-;-c, ). W. Kaim, W. Bruns et al., Angew. Chem. Int. Ed, vol.90, pp.3659-3853, 1990.

M. D. Ward, Chem. Soc. Rev, vol.24, pp.842-851, 1995.

R. P. Houser, V. G. Young, and W. B. Tolman, J. Am. Chem. Soc, vol.118, pp.2101-2102, 1996.

J. Gennari, S. Pécaut, F. Debeer, M. Neese, C. Collomb et al., Angew. Chem. Int. Ed, vol.50, pp.5662-5666, 2011.

M. Robin and D. Peter, Adv. Inorg. Chem. Radiochem, vol.10, pp.5-14, 1967.

K. Brown, K. Djinovic-carugo, T. Haltia, I. Cabrito, M. Saraste et al., Acta Crystallographica Section F, vol.275, pp.234-237, 2000.

S. Torelli, M. Orio, J. Pécaut, H. Jamet, L. L. Pape et al., Angew. Chem. Int. Ed, vol.49, pp.4774-4784, 2010.

J. Kuzelka, S. Mukhopadhyay, B. Spingler, and S. J. Lippard, Inorg. Chem, vol.43, pp.1751-1761, 2004.

J. R. Hagadorn, T. I. Zahn, L. Que, and W. B. Tolman, Dalton Trans, pp.1790-1794, 2003.