Onset of three-centre, four-electron bonding in peri-substituted acenaphthenes: A structural and computational investigation

被引:41
作者
Aschenbach, Lara K. [1 ]
Knight, Fergus R. [1 ]
Randall, Rebecca A. M. [1 ]
Cordes, David B. [1 ]
Baggott, Alex [1 ]
Buehl, Michael [1 ]
Slawin, Alexandra M. Z. [1 ]
Woollins, J. Derek [1 ]
机构
[1] Univ St Andrews, Sch Chem, St Andrews, Fife, Scotland
基金
英国工程与自然科学研究理事会;
关键词
CHALCOGEN-CHALCOGEN INTERACTIONS; NONBONDED ATOMIC CONTACTS; 1ST LINEAR ALIGNMENT; CENTER-DOT-P; X-RAY; NEUTRON-DIFFRACTION; MOLECULAR-STRUCTURE; CRYSTAL-STRUCTURE; LONE-PAIR; THEORETICAL INVESTIGATIONS;
D O I
10.1039/c1dt11697e
中图分类号
O61 [无机化学];
学科分类号
070301 ; 081704 ;
摘要
Two series of sterically crowded peri-substituted acenaphthenes have been prepared, containing mixed halogen-chalcogen functionalities at the 5,6-positions in A1-A6 (Acenap[X][EPh] (Acenap = acenaphthene-5,6-diyl; X = Br, I; E = S, Se, Te) and chalcogen-chalcogen moieties in A7-A12 (Acenap [EPh][E'Ph] (Acenap = acenaphthene-5,6-diyl; E/E' = S, Se, Te). The related dihalide compounds A13-A16 Acenap[XX'] (XX' = BrBr, II, IBr, ClCl) have also been prepared. Distortion of the acenaphthene framework away from the ideal was studied as a function of the steric bulk of the interacting halogen and chalcogen atoms occupying the peri-positions. The acenaphthene series experiences a general increase in peri-separation for molecules accommodating heavier congeners and maps the trends observed previously for the analogous naphthalene compounds N1-N12 (Nap[X][EPh], Nap[EPh][E'Ph] (X = Br, I; E/E' = S, Se, Te). The conformation of the aromatic ring systems and subsequent location of p-type lone-pairs dominates the geometry of the peri-region. The differences in peri-separations observed for compounds adopting differing conformations of the peri-substituted phenyl group can be correlated to the ability of the frontier orbitals of the halogen or chalcogen atoms to take part in attractive or repulsive interactions. Density-functional studies have confirmed these interactions and suggested the onset of formation of three-centre, four-electron bonding under appropriate geometric conditions.
引用
收藏
页码:3141 / 3153
页数:13
相关论文
共 128 条
[1]  
ALDER RW, 1968, CHEM COMMUN, P723
[2]   TABLES OF BOND LENGTHS DETERMINED BY X-RAY AND NEUTRON-DIFFRACTION .1. BOND LENGTHS IN ORGANIC-COMPOUNDS [J].
ALLEN, FH ;
KENNARD, O ;
WATSON, DG ;
BRAMMER, L ;
ORPEN, AG ;
TAYLOR, R .
JOURNAL OF THE CHEMICAL SOCIETY-PERKIN TRANSACTIONS 2, 1987, (12) :S1-S19
[3]   CONFORMATIONS AND ROTATION BARRIERS IN 1,8-BIS(TRIMETHYLELEMENT)NAPHTHALENES [J].
ANET, FAL ;
DONOVAN, D ;
SJOSTRAND, U ;
COZZI, F ;
MISLOW, K .
JOURNAL OF THE AMERICAN CHEMICAL SOCIETY, 1980, 102 (05) :1748-1749
[4]   BONDING BETWEEN NONBONDED SULFUR AND OXYGEN-ATOMS IN SELECTED ORGANIC-MOLECULES (A QUANTUM CHEMICAL STUDY) [J].
ANGYAN, JG ;
POIRIER, RA ;
KUCSMAN, A ;
CSIZMADIA, IG .
JOURNAL OF THE AMERICAN CHEMICAL SOCIETY, 1987, 109 (08) :2237-2245
[5]   THE REACTION OF SULFUR WITH DILITHIO COMPOUNDS - THE SYNTHESES AND STRUCTURES OF PHENANTHRO[1,10-CD]-1,2-DITHIOLE AND PHENANTHRO[4,5-CDE][1,2]DITHIIN [J].
ASHE, AJ ;
KAMPF, JW ;
SAVLA, PM .
HETEROATOM CHEMISTRY, 1994, 5 (02) :113-119
[6]   SELECTIVE FUNCTIONALIZATION IN THE BAY REGION OF POLYCYCLIC AROMATIC-HYDROCARBONS VIA DILITHIATION [J].
ASHE, AJ ;
KAMPF, JW ;
SAVLA, PM .
JOURNAL OF ORGANIC CHEMISTRY, 1990, 55 (21) :5558-5559
[7]   Platinum complexes of dibenzo[1,2]dithiin, dibenzo[1,2]dithiin oxides and related polyaromatic hydrocarbon ligands [J].
Aucott, SM ;
Kilian, P ;
Robertson, SD ;
Slawin, AMZ ;
Woollins, JD .
CHEMISTRY-A EUROPEAN JOURNAL, 2006, 12 (03) :895-902
[8]   Bis(cyclopentadienyl)titanium complexes of naphthalene-1,8-dithiolates, biphenyl 2,2′-dithiolates, and related ligands [J].
Aucott, SM ;
Kilian, P ;
Milton, HL ;
Robertson, SD ;
Slawin, AMZ ;
Woollins, JD .
INORGANIC CHEMISTRY, 2005, 44 (08) :2710-2718
[9]   Crystal structures and molecular modeling of 1,8 chalcogenide-substituted naphthalenes [J].
Aucott, SM ;
Milton, HL ;
Robertson, SD ;
Slawin, AMZ ;
Woollins, JD .
HETEROATOM CHEMISTRY, 2004, 15 (07) :530-542
[10]   The preparation and characterisation of bimetallic iridium(II) complexes containing derivatised bridging naphthalene-1,8-disulfur or 4,5-dithiolato acephenanthrylene ligands [J].
Aucott, SM ;
Milton, HL ;
Robertson, SD ;
Slawin, AMZ ;
Woollins, JD .
DALTON TRANSACTIONS, 2004, (20) :3347-3352