Nature of the E⋯E′ interactions (E, E′ = O, S, Se, and Te) at naphthalene 1, 8-positions with fine details of the structures: experimental and theoretical investigations. (23rd August 2019)

• Record Type: Journal Article
• Authors: Hayashi, Satoko; Uegaito, Manabu; Nishide, Taro; Tanaka, Eiichiro; Nakanishi, Waro; Sasamori, Takahiro; Tokitoh, Norihiro; Minoura, Mao
• Is Part Of: New journal of chemistry. Volume 43:Number 36(2019)
• Page Start: 14224
• Page End: 14237
• Publication Date: 2019-08-23
• Subjects: Chemistry -- Periodicals; Chimie -- Périodiques; 540
• DOI: 10.1039/c9nj02198a
• Languages: English
• ISSNs: 1144-0546

Abstract

Abstract : The nature of E⋯E′ in 1-RE–8-R′E′C10 H6 (E/E′ = O, S, Se and Te) is clarified with the QTAIM approach and NBO analysis, after structural determinations. Abstract : The intrinsic dynamic and static natures of the E⋯E′ interactions at the 1, 8-positions of 1-(MeE)–8-(MeE′)C10 H6 [1a–1f (E ≠ E′) and1g–1j (E = E′)] were elucidated with QTAIM-DFA, after structural determination of 1-(PhE)–8-(PhE′)C10 H6 (3a–3f ), where (E, E′:x ) = (O, S:a ), (O, Se:b ), (O, Te:c ), (S, Se:d ), (S, Te:e ), (Se, Te:f ), (O, O:g ), (S, S:h ), (Se, Se:i ) and (Te, Te:j ) ( χ E ≥ χ E′ ). While theAB structures are confirmed for3a, 3b and3d–3f, which consist of the np (E)⋯σ*(E′–CPh ) interactions, the structure wasBB for3c, where the E–CR /E′–CR (R = Ph) bond is perpendicular to the naphthyl plane inA and it is placed on the plane inB . While theAB structures are determined by the p(E)–π(Ph) conjugations, theBB structure is by the crystal packing effect. TheBA structure with np (E′)⋯σ*(E–CPh ) was not detected. While the nature of a typical hydrogen bond with covalency was predicted forBB, AA andBA, with the CT-MC (molecular complex formation through charge transfer) nature forAB in1e and1f (R = Me for E–CR /E′–CR ), the CT-MC nature was predicted for all conformers of1j, for example. NBO analysis for1a–1f revealed that the acceptor orbitals contribute much more than the donor orbitals and the order is σ*(O–CMe : <0.5 kcal mol −1 ) ≪ σ*(S–CMe : ≈5 kcal mol −1 ) ≪ σ*(Se–CMe : ≈10 kcal mol −1 ) ≪ σ*(Te–CMe : ≈16 kcal mol −1 ) for np (S), np (Se) and np (Te). The E (2) values proportionally correlate to C ii −1 forAB and/orBA of1a–1j, if analyzed separately for σ*(S–C), σ*(Se–C) and σ*(Te–C).