Famous but Unknown: Structural Characterization of the Ruthenium-MACHO Catalyst

Abstract

In this work, we present the determination of the crystal structure of the widely used transition-metal complex known as ruthenium-MACHO. The crystal structure of the selectively formed product of the reaction between this complex and hydrogen chloride dissolved in chloroform was also evaluated. The structures determined in this work were compared and evaluated by using various spectroscopic techniques.

Key words

ruthenium catalyst - ruthenium-MACHO - pincer complexes - coordination chemistry - structure determination - crystal structure

• References and Notes

• 1a Kuriyama W, Matsumoto T, Ogata O, Ino Y, Aoki K, Tanaka S, Ishida K, Kobayashi T, Sayo N, Saito T. Org. Process Res. Dev. 2012; 16: 166
• 1b Takeuchi Y, Mitunari S. WO 2011048757, 2011
• 2a Kothandaraman J, Goeppert A, Czaun M, Olah GA, Prakash GK. S. J. Am. Chem. Soc. 2016; 138: 778
• 2b Kar S, Goeppert A, Prakash GK. S. J. Am. Chem. Soc. 2019; 141: 12518
• 3a Nielsen M, Alberico E, Baumann W, Drexler H.-J, Junge H, Gladiali S, Beller M. Nature 2013; 495: 85
• 3b Kaithal A, Chatterjee B, Werlé C, Leitner W. Angew. Chem. Int. Ed. 2021; 60: 26500
• 4 Nielsen M, Junge H, Kammer A, Beller M. Angew. Chem. Int. Ed. 2012; 51: 5711
• 5 Thiyagarajan S, Gunanathan C. J. Am. Chem. Soc. 2019; 141: 3822
• 6 Thiyagarajan S, Gunanathan C. ACS Catal. 2018; 8: 2473
• 7 Ni Z, Padilla R, dos Santos Mello L, Nielsen M. ACS Catal. 2023; 13: 5449
• 8 Padilla R, Jørgensen MS. B, Paixão MW, Nielsen M. Green Chem. 2019; 21: 5195
• 9 Kothandaraman J, Czaun M, Goeppert A, Haiges R, Jones J.-P, May RB, Prakash GK. S, Olah GA. ChemSusChem 2015; 8: 1442
• 10a Ramaraj A, Nethaji M, Jagirdar BR. Dalton Trans. 2014; 43: 14625
• 10b Garbe M, Wei Z, Tannert B, Spannenberg A, Jiao H, Bachmann S, Scalone M, Junge K, Beller M. Adv. Synth. Catal. 2019; 361: 1913
• 10c Zhang L, Nguyen DH, Raffa G, Trivelli X, Capet F, Desset S, Paul S, Dumeignil F, Gauvin RM. ChemSusChem 2016; 9: 1413
• 11 Anaby A, Schelwies M, Schwaben J, Rominger F, Hashmi AS. K, Schaub T. Organometallics 2018; 37: 2193
• 12 Herzfeld J, Berger AE. J. Chem. Phys. 1980; 73: 6021
• 13 Karplus M. J. Am. Chem. Soc. 1963; 85: 2870
• 14 Zhang L, Raffa G, Nguyen DH, Swesi Y, Corbel-Demailly L, Capet F, Trivelli X, Desset S, Paul S, Paul J.-F, Fongarland P, Dumeignil F, Gauvin RM. J. Catal. 2016; 340: 331
• 15 CCDC 2448204 contains the supplementary crystallographic data for Ru-MACHO. The data can be obtained free of charge from The Cambridge Crystallographic Data Centre via www.ccdc.cam.ac.uk/structures
• 16 Spek AL. Acta Crystallogr., Sect. C: Struct. Chem. 2015; 71: 9
• 17a Kleemiss F, Dolomanov OV, Bodensteiner M, Peyerimhoff N, Midgley L, Bourhis LJ, Genoni A, Malaspina LA, Jayatilaka D, Spencer JL, White F, Grundkötter-Stock B, Steinhauer S, Lentz D, Puschmann H, Grabowsky S. Chem. Sci. 2021; 12: 1675
• 17b Fugel M, Jayatilaka D, Hupf E, Overgaard J, Hathwar VR, Macchi P, Turner MJ, Howard JA. K, Dolomanov OV, Puschmann H, Iversen BB, Bürgi H.-B, Grabowsky S. IUCrJ 2018; 5: 32
• 18 Dolomanov OV, Bourhis LJ, Gildea RJ, Howard JA. K, Puschmann H. J. Appl. Crystallogr. 2009; 42: 339
• 19a Alberico E, Lennox AJ. J, Vogt LK, Jiao H, Baumann W, Drexler H.-J, Nielsen M, Spannenberg A, Checinski MP, Junge H, Beller M. J. Am. Chem. Soc. 2016; 138: 14890
• 19b Smith SA. M, Lagaditis PO, Lüpke A, Lough AJ, Morris RH. Chem. Eur. J. 2017; 23: 7212
• 19c Maser L, Schneider C, Vondung L, Alig L, Langer R. J. Am. Chem. Soc. 2019; 141: 7596
• 20 Nguyen DH, Mwerel D, Merle N, Trivelli X, Capet F, Gauvin RM. Dalton Trans. 2021; 50: 10067
• 21 Chen T, Li M, Liu J. Cryst. Growth Des. 2018; 18: 2765