Issue 12, 2001

The synthesis of closo- and nido-(aminoalkyl)dicarbaboranes: a re-examination of contradictory literature reports, crystal structure of [7-{H3N(CH2)3}-7,8-C2B9H11]·NH2NH2

Abstract

The reaction of Li[1-tBuMe2Si-1,2-C2B10H10] with N-(bromoethyl)phthalimide or N-3-(bromopropyl)phthalimide generates unusual carboranyl heterocycles, resulting from nucleophilic substitution followed by insertion of a phthalimide carbonyl into the C–Si bond. The structure of one was determined by single crystal X-ray diffraction. Reaction of the heterocycles with nBu4NF affords closo-1-{C6H4(CO)2N(CH2)n}-1,2-C2B10H11 (1bn = 2 and 1cn = 3) together with the anions nido-[7-{C6H4(CO)2N(CH2)n}-7,8-C2B9H11] as minor side-products on prolonged reaction. The prolonged reaction of 1b and 1c with hydrazine results in deboronation to give hydrazine solvates of zwitterionic nido-[7-{H3N(CH2)n}-7,8-C2B9H11]. A single crystal X-ray diffraction study for one reveals an elegant dimeric architecture supported by hydrazine-bridged hydrogen bonds. The reaction of the heterocycles with ethanolic KOH results in cluster deboronation and partial deprotection of the amine group to give nido-[7-(2-O2CC6H4CONH)(CH2)n-7,8-C2B9H11]2− as potassium salts which can be metathesised to less hygroscopic Me3NH+ salts. The molecular structure of one of the latter displays hydrogen bonding generating a dimeric unit. Complete deprotection of the amine function in these salts by water–HCl gives zwitterionic aminoalkylcarboranes nido-7-{H3N(CH2)n}-7,8-C2B9H11.

Graphical abstract: The synthesis of closo- and nido-(aminoalkyl)dicarbaboranes: a re-examination of contradictory literature reports, crystal structure of [7-{H3N(CH2)3}-7,8-C2B9H11]·NH2NH2 [ ]

Supplementary files

Article information

Article type
Paper
Submitted
02 Mar 2001
Accepted
01 May 2001
First published
25 May 2001

J. Chem. Soc., Dalton Trans., 2001, 1820-1826

The synthesis of closo- and nido-(aminoalkyl)dicarbaboranes: a re-examination of contradictory literature reports, crystal structure of [7-{H3N(CH2)3}-7,8-C2B9H11]·NH2NH2

A. S. Batsanov, A. E. Goeta, J. A. K. Howard, A. K. Hughes and J. M. Malget, J. Chem. Soc., Dalton Trans., 2001, 1820 DOI: 10.1039/B102009I

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