STRUCTURES OF MOLECULES WITH CHARGE EXCITATION OR STERIC PACKING .17. STRUCTURAL-CHANGES ON REDUCTION OF 9-(DIPHENYLMETHYLIDENE)FLUORENE BY SODIUM METAL TO SHEETS OF (R2O)NA-CIRCLE-PLUS-CONNECTED HYDROCARBON DIANIONS

被引：19

作者：

BOCK, H ^{[1
]}

RUPPERT, K ^{[1
]}

HERDTWECK, E ^{[1
]}

HERRMANN, WA ^{[1
]}

机构：

[1] TECH UNIV MUNICH,INST ANORGAN CHEM,W-8046 GARCHING,GERMANY

来源：

HELVETICA CHIMICA ACTA | 1992年 / 75卷 / 06期

关键词：

D O I：

10.1002/hlca.19920750607

中图分类号：

O6 [化学];

学科分类号：

0703 ;

摘要：

The single-crystal structure of 9-(diphenylmethylidene)fluorene (monoclinic, space group P2(1)/n, Z = 4) proves a C=C bond length of 135 pm and a twisting of the two Ph rings out of the methylidene-fluorene plane by 70-degrees and 83-degrees. Its reduction in Et2O solution by a Na mirror under Ar yields dark green crystals with a metallic luster. Their structure, determined in a N2 flow cooled to 223 K (monoclinic, space group C2/c, Z = 4), reveals sheets of hydrocarbon dianions, connected by sodium(diethylether) links. The Na centers arc sixfold coordinated as half-sandwiches to the fluorene benzo rings and threefold allylic to the Ph rings. In the dianion of 9-(diphenylmethylidene)fluorene, the central C=C bond is stretched by 13 pm to 148 pm length, and the two molecular cyanine-like halves are twisted by 51-degrees relative to each other. Both the contact-ion multiple structures as well as the structural changes on twofold reduction are discussed by way of comparison with literature examples and based on semiempirical calculations.

引用

页码：1816 / 1824

页数：9

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