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The interdigitated and layered structures of the tetraalkylferrocenium salts [DEC][CB 11 H 12 ], [DEC] 2 [B 12 F 12 ], [DEC][BF 4 ], [DEC][PF 6 ], and [DEC][ClO 3 ] were determined by single-crystal X-ray diffraction (DEC + = 1,1′,3,3′-tetrakis(2-methyl-2-nonyl)ferrocenium(1+)). The structures of the salts of the two smaller anions were similar to the previously published oxoanion structures of [DEC][XO n − ] (XO n −  = NO 3 − , ClO 4 − , and ReO 4 − ), with layers of trigonal-pyramidal ClO 3 − or tetrahedral BF 4 − anions stuffed between layers of interdigitated ferrocenium ions. The DEC + cations in structures with the more highly charged and/or larger anions B 12 F 12 2− , CB 11 H 12 − , and PF 6 − are also layered but the interdigitation is not as regular and not as complete as in the structures with relatively small 1− anions. Other differences and similarities of the eight [DEC] n [X] structures ( n  = 1, 2) are discussed. [ABSTRACT FROM AUTHOR]

Multiple variations of the reaction conditions reported in 1964 for the diamination of K 2 B 12 H 12 (potassium dodecahydro- closo -dodecaborate(2−)) with hydroxylamine- O -sulfonic acid were studied to improve the isolated yields of the three isomers of B 12 H 10 (NH 3 ) 2 . Screening the sets of reaction conditions without completely working up each of the reaction mixtures, and therefore without the lengthy separation and isolation of the individual B 12 H 10 (NH 3 ) 2 isomers for each reaction mixture, was possible by recording 1 H- 15 N HSQC NMR spectra of the crude reaction mixtures. The 1 H-dimension of these spectra exhibited narrow, baseline separated resonances for 1,2-, 1,7- and 1,12-B 12 H 10 (NH 3 ) 2 and for the B 12 H 11 (NH 3 ) − intermediate, allowing their relative concentrations to be determined to the nearest percent. The best synthetic conditions resulted in 9, 25, and 6% isolated yields of 1,2-, 1,7- and 1,12-B 12 H 10 (NH 3 ) 2 , respectively. The decafluoro derivatives 1,2-, 1,7-, and 1,12-B 12 F 10 (NH 3 ) 2 were prepared for the first time by direct fluorination of the B 12 H 10 (NH 3 ) 2 isomers, either individually or as a mixture subsequently separated by column chromatography similar to the separation and purification of the B 12 H 10 (NH 3 ) 2 isomers. The structures of 1,7-B 12 F 10 (NH 2 ) 2 ·4CH 3 CONH 2 , 1,12-B 12 F 10 (NH 2 ) 2 ·6CH 3 CONH 2 , 1,2-B 12 H 10 (NH 2 ) 2 ·1.5CH 3 CO 2 CH 2 CH 3 , 1,7-B 12 H 10 (NH 2 ) 2 ·1.23H 2 O, 1,12-B 12 H 10 (NH 2 ) 2 ·2CH 3 CN, and solvent-free 1,12-B 12 H 10 (NH 2 ) 2 were determined by single-crystal X-ray diffraction. [ABSTRACT FROM AUTHOR]