Abstract
The geometrical twist of aryl-aryl bond in biphenyl by weakly coordinating anion and selone at the para position has not been clear so far. We report here the synthesis and investigation into the diverse structural properties of biphenyl with weakly coordinating biphenyl imidazolium salts and neutral imidazole selone that exhibit three atropisomers of biphenyl. The approaches underline the diversity of the effects of para substituent with dynamic nature at biphenyl molecule.
Graphical Abstract
SYNOPSIS The synthesis and investigation into the diverse structural properties of three atropisomers of biphenyl tuned by para substituted weakly coordinating imidazolium salts and neutral imidazole selone are reported.
This is a preview of subscription content, log in via an institution to check access.
Similar content being viewed by others
References
Kudernac T, Ruangsupapichat N, Parschau M, Maciá B, Katsonis N, Harutyunyan S R, Ernst K and Feringa B L 2011 Electrically driven directional motion of a four-wheeled molecule on a metal surface Nature 479 208
Chuhmanov E P, Ermolaev N L, Plakhutin B N and Ignatov S K 2018 Tris(perfluoroalkyl)germylethynyl derivatives of biphenyl containing ferrocenyl donor group: Structure, spectra, and photoinduced intramolecular electron transfer comput Theor. Chem. 1123 50
Maier F and Trapp O 2013 The stereodynamics of 5,5\(^{\prime }\)-disubstituted BIPHEPs Chirality 25 126
Fischer F, Siegle A F, Checinski M, Fischer C, Kral K, Thede R, Trapp O and Hapke M 2016 Synthesis of naphthylpyridines from unsymmetrical naphthylheptadiynes and the configurational stability of the biaryl axis J. Org. Chem. 81 3087
Bastiansen O and Samdal S 1985 Structure and barrier of internal rotation of biphenyl derivatives in the gaseous state: Part 4. Barrier of internal rotation in biphenyl, perdeuterated biphenyl and seven non-ortho-substituted halogen derivatives J. Mol. Struct. 128 115
Almenningen A, Bastiansen O, Fernholt L, Cyvin B N, Cyvin S J and Samdal S 1985 Structure and barrier of internal rotation of biphenyl derivatives in the gaseous state: Part 1. The molecular structure and normal coordinate analysis of normal biphenyl and pedeuterated biphenyl J. Mol. Struct. 128 59
Charbonneau G P and Delugeard Y 1976 Structural transition in polyphenyls. III. Crystal structure of biphenyl at 110 K Acta Crystallogr. B32 1420
Cailleau H, Girard A, Moussa F and Zeyen C M E 1979 Inelastic neutron scattering study of structural phase transitions in polyphenyls Solid State Commun. 29 259
Barton D H R 1970 The principles of conformational analysis Science 169 539
Grein F 2002 Twist angles and rotational energy barriers of biphenyl and substituted biphenyls J. Phys. Chem. A 106 3823
Mazzanti A, Lunazzi L, Minzoni M and Anderson J E 2006 Rotation in biphenyls with a single ortho-substituent J. Org. Chem. 71 5474
Masson E 2013 Torsional barriers of substituted biphenyls calculated using density functional theory: a benchmarking study Org. Biomol. Chem. 11 2859
Lorentzen M, Kalvet I, Sauriol F, Rantanen T, Jørgensen K B and Snieckus V 2017 Atropisomerism in tertiary biaryl 2-amides: A study of Ar–CO and Ar–Ar’ rotational barriers J. Org. Chem. 82 7300
Bihlmeier A, Rotzler J, Rickhaus M, Mayor M and Klopper W 2015 Activation enthalpies and entropies of the atropisomerization of substituted butyl-bridged biphenyls Phys. Chem. Chem. Phys. 17 11165
Perrin D D and Armarego W L F 1988 In Purification of laboratory chemicals 3\(^{\rm rd}\) edn. (London: Pergamon Press)
Dolomanov O V, Bourhis L J, Gildea R J, Howard J A K and Puschmann H 2009 OLEX2: a complete structure solution, refinement and analysis program J. Appl. Cryst. 42 339
Burla M C, Caliandro R, Camalli M, Carrozzini B, Cascarano G L, De Caro L, Giacovazzo C, Polidori G, Siliqi D and Spagna R 2007 IL MILIONE: a suite of computer programs for crystal structure solution of proteins J. Appl. Cryst. 40 609
Bourhis L J, Dolomanov O V, Gildea R J, Howard J A K and Puschmann H 2015 The anatomy of a comprehensive constrained, restrained refinement program for the modern computing environment-Olex2 Dissected Acta Cryst. A71 59
Nelson D J, Collado A, Manzini S, Meiries S, Slawin, A M Z, Cordes D B and Nolan S P 2014 Methoxy-functionalized N-heterocyclic carbenes Organometallics 33 2048
(a) Tretiakov M, Shermolovich Y G, Singh A P, Samuel P P, Roesky H W, Niepötter B, Visschera A and Stalke D 2013 Lewis-base stabilized diiodine adducts with N-heterocyclic chalcogenamides Dalton Trans. 42 12940; (b) Nelson D J, Collado A, Manzini S, Meiries S, Slawin A M Z, Cordes D B and Nolan S P Methoxy-Functionalized N-Heterocyclic Carbenes Organometallics 33 2048 ; (c) Srinivas K, Suresh P, Babu C N, Sathyanarayana A and Prabusankar G 2015 Heavier chalcogenone complexes of bismuth(III)trihalides: Potential catalysts for acylative cleavage of cyclic ethers RSC Adv. 5 15579
Sathyanarayana A, Srinivas K, Mandal A, Gharami S and Prabusankar G 2014 Synthesis, spectral and structural properties of bis-imidazole selones J. Chem. Sci. 126 1589
Aldridge B, De Luca G, Edgar M, Emsley J W, Furby M I C and Webster M 1998 The structure of 2,2\(^{\prime }\)-difluorobiphenyl in solid crystalline and liquid crystalline phases Liq. Cryst. 24 569
Acknowledgements
We gratefully acknowledge the CSIR, New Delhi (01(2884)/17/EMR-II) for financial support. RK thanks UGC for the fellowship.
Author information
Authors and Affiliations
Corresponding author
Additional information
Special Issue on Modern Trends in Inorganic Chemistry.
Electronic supplementary material
Below is the link to the electronic supplementary material.
Rights and permissions
About this article
Cite this article
Karupnaswamy, R., Ganesan, P. Three atropisomers of biphenyl: twist by tunable para substituents. J Chem Sci 130, 82 (2018). https://doi.org/10.1007/s12039-018-1482-8
Received:
Revised:
Accepted:
Published:
DOI: https://doi.org/10.1007/s12039-018-1482-8