Diiodoacetylene: compact, strong ditopic halogen bond donor
Diiodoacetylene: compact, strong ditopic halogen bond donor
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二碘乙炔：紧凑、强双位卤素键供体
DOI：
10.1039/c2ce00029f
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发表时间：
2012
期刊：
影响因子：
3.1
通讯作者：
L. Brammer
中科院分区：
文献类型：
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作者：
Catherine Perkins;Stefano Libri;H. Adams;L. Brammer
二碘乙炔，C2 I2，是除了I2或其他二卤素之外最小的双配位卤素键供体。介绍了一种由Sonagashira偶联试剂Me_3SiO_2CH合成二碘乙炔的简便方法。本文报道了C_2I_2与二甲基甲酰胺（DMF）、吡嗪（pyz）和1，4-二氮杂双环辛烷（dabco）的卤素键合加合物的X-射线晶体学表征。它们都采用一维卤素键合链，通过短C-I O [I O 2.834（4）-2.888（4）A; C-I O > 170°]或C-I N [I N 2.715（3）-2.832（7）A; C-I N > 175°]相互作用连接。尝试合成C2 I2与六亚甲基四胺（hCl 4）的加合物导致C2 I4·hCl 4的加合物的分离和晶体学表征，表明C2 I2在溶液中分解产生C2 I4。该加合物包含两个独立的C2 I4分子，它们分别作为四配位和二配位卤键供体形成C-I N相互作用[I N 2.948（7）-2.999（8）A; C-I N > 165°]，占据htma上四个氮位点中的三个。其余的氮位点参与N → C（π）相互作用，该相互作用与ditopic C2 I4分子的平面正交。对二碘（聚）炔I（C C）nI（n = 1-3）和C2 I 4分子形成的卤键的单独研究表明，当归一化为货车德瓦尔斯半径时，C-I N卤键较短，并且通过推断，比涉及其他受体基团的卤键更强，并证明Csp-I N卤键通常较短Csp 2-I N卤键。
Diiodoacetylene, C2I2, is the smallest ditopic halogen bond donor other than I2 or other dihalogens. A convenient synthesis of diiodoacetylene from the common Sonagashira coupling reagent Me3SiC≡CH, is described. The halogen-bonded adducts of C2I2 with dimethylformamide (DMF), pyrazine (pyz) and 1,4-diazabicyclooctane (dabco) have been characterised by X-ray crystallography. All adopt 1D halogen-bonded chains linked via short C–I⋯O [I⋯O 2.834(4)–2.888(4) A; C–I⋯O > 170°] or C–I⋯N [I⋯N 2.715(3)–2.832(7) A; C–I⋯N > 175°] interactions. Attempts to synthesise the adduct of C2I2 with hexamethylenetetramine (hmta) resulted in isolation and crystallographic characterisation of the adduct of C2I4·hmta, indicating decomposition of C2I2 to yield C2I4 in solution. The adduct comprises two independent C2I4 molecules that act, respectively, as tetratopic and ditopic halogen bond donors forming C–I⋯N interactions [I⋯N 2.948(7)–2.999(8) A; C–I⋯N > 165°], occupying three of the four nitrogen sites on htma. The remaining nitrogen sites engage in N⋯C(π) interactions directed orthogonal to the plane of the ditopic C2I4 molecules. Separate surveys of halogen bonds formed by diiodo(poly)alkynes I(C≡C)nI (n = 1–3) and by C2I4 molecules indicate that C–I⋯N halogen bonds are shorter, when normalised for van der Waals radii, and, by inference, stronger than halogen bonds involving other acceptor groups, and demonstrates that Csp–I⋯N halogen bonds are generally shorter Csp2–I⋯N halogen bonds.
影响因子：
4.9
作者：
C. Präsang;A. Whitwood;D. Bruce
通讯作者：
C. Präsang;A. Whitwood;D. Bruce
DOI：
10.1073/pnas.0407607101
发表时间：
2004-11-30
影响因子：
11.1
作者：
Auffinger, P;Hays, FA;Ho, PS
通讯作者：
Ho, PS
DOI：
10.1107/s0108767394005726
发表时间：
1995-01-01
期刊：
ACTA CRYSTALLOGRAPHICA SECTION A
影响因子：
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作者：
BLESSING, RH
通讯作者：
BLESSING, RH