Interactions in crystals .99. Akali-metal contact-ion multiples of acenaphthylene and fluoranthene dianions: Five-membered and six-membered ring coordination
Interactions in crystals .99. Akali-metal contact-ion multiples of acenaphthylene and fluoranthene dianions: Five-membered and six-membered ring coordination
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DOI：
10.1016/0022-328x(95)06063-3
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发表时间：
1996-08-09
影响因子：
2.3
通讯作者：
Nather, C
中科院分区：
文献类型：
--
作者：
Bock, H;Arad, C;Nather, C
在定性MO考虑的刺激下，非交替π-烃苊和荧蒽在非质子条件下在其醚溶液中被碱金属还原为其二价阴离子。这些结晶为不同结构的接触离子倍数：苊的(15-冠-5)-溶剂化钠盐是单体接触离子三重[(H2CH2CO)(5)Na+C12H8++Na+(OCH2CH2)5](1)，在环戊二烯基环上方和下方具有十倍配位的Na+抗衡阳离子。相比之下，荧蒽二价阴离子的DME-或二甘醇二甲醚溶剂化的Na+-和Li+-盐[(R(2)O)(2)Me(+)C(16)H(10)(++)Me(+)(OR(2))(2)]无限结晶在含有八倍配位Li+或十倍配位Na+抗衡阳离子的聚合物串中，高于和低于两个萘六元结构的不同戒指。对于这些相当意想不到的配位差异，MNDO 基于结构数据的计算提供了一个合理的理由：苊二价阴离子中的负电荷主要位于五元环内，荧蒽二价阴离子中的负电荷主要位于萘六元环内。
Stimulated by qualitative MO considerations, the non-alternant pi-hydrocarbons acenaphthylene and fluoranthene have been reduced in their ether solutions under aprotic conditions by alkali metals to their dianions. These crystallize as contact ion multiples of different structures: the (15-crown-5)-solvated sodium salt of acenaphthylene is a monomeric contact ion triple [(H2CH2CO)(5)Na+C12H8++Na+(OCH2CH2)5](1) with the ten-fold coordinated Na+ counter cations above and below the cyclopentadienyl ring. In contrast, the DME- or diglyme-solvated Na+- and Li+-salts of fluoranthene dianion [(R(2)O)(2)Me(+)C(16)H(10)(++)Me(+)(OR(2))(2)]infinity crystallize in polymer strings containing eight-fold coordinated Li+ or ten-fold coordinated Na+ counter cations above and below different of the two naphthalene six-membered rings. For these rather unexpected coordination differences, MNDO calculations based on the structural data provide a plausible rationale: the negative charge in the acenaphthylene dianion is predominantly located within the five-membered ring and in the fluoranthene dianion within the naphthalene six-membered rings.