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Title: Reactions of nido-6-SB[sub 9]H[sub 11] with imines. Structural characterization of endo-9-((t-Bu)MeC=NH)-arachno-6-SB[sub 9]H[sub 11]

Abstract

The reaction of nido-6-SB[sub 9]H[sub 11] with N-tert-butylformaldimine results in the formation of the unique zwitterionic compound 9-((t-Bu)NH[sub 2][sup +]CH[sub 2])-nido-6-SB[sub 9]H[sub 9][sup [minus]] (1). The formation of 1 is consistent with a reaction sequence involving hydroboration of the imine at the B9 cage position accompanied by transfer of a proton from a cage-bridging site to the nitrogen atom. When 1 is then reacted with acetonitrile, a rearrangement occurs and the adduct exo-9-(CH[sub 3]CN)-endo-9-((t-Bu)NHCH[sub 2])-arachno-6-SB[sub 9]H[sub 10] (2) is formed. The reaction of nido-6-SB[sub 9]H[sub 11] with tert-butylmethylketimine (4) gives the substituted imine product endo-9-((t-Bu)MeC=NH)-arachno-6-SB[sub 9]H[sub 11] (6). A single-crystal x-ray study of 6 confirmed that the imine adopts an endo position with regard to the arachno-6-SB[sub 9]H[sub 11] framework. Furthermore, the observed imine hydrogen to cage sulfur distance (2.712 (28) [angstrom]) is less than the sum of the van der Waals radii of hydrogen and sulfur, suggesting that the observed endo configuration may be stabilized by N-H---S hydrogen-bonding interactions. Thermolysis of 6 results in hydrogenation and rearrangement of the imine group to produce exo-9-((t-Bu)MeC(H)NH[sub 2])-arachno-6-SB[sub 9]H[sub 11] (7).

Authors:
; ;  [1]
  1. Univ. of Pennsylvania, Philadelphia (United States)
Publication Date:
OSTI Identifier:
7186879
Resource Type:
Journal Article
Journal Name:
Inorganic Chemistry; (United States)
Additional Journal Information:
Journal Volume: 31:24; Journal ID: ISSN 0020-1669
Country of Publication:
United States
Language:
English
Subject:
37 INORGANIC, ORGANIC, PHYSICAL AND ANALYTICAL CHEMISTRY; BORON HYDRIDES; CHEMICAL REACTIONS; IMINES; CRYSTAL STRUCTURE; EXPERIMENTAL DATA; MOLECULAR STRUCTURE; THERMAL DEGRADATION; X-RAY DIFFRACTION; BORON COMPOUNDS; COHERENT SCATTERING; DATA; DIFFRACTION; HYDRIDES; HYDROGEN COMPOUNDS; INFORMATION; NUMERICAL DATA; ORGANIC COMPOUNDS; ORGANIC NITROGEN COMPOUNDS; SCATTERING; 400201* - Chemical & Physicochemical Properties

Citation Formats

Kuepper, S, Carroll, P J, and Sneddon, L G. Reactions of nido-6-SB[sub 9]H[sub 11] with imines. Structural characterization of endo-9-((t-Bu)MeC=NH)-arachno-6-SB[sub 9]H[sub 11]. United States: N. p., 1992. Web. doi:10.1021/ic00050a006.
Kuepper, S, Carroll, P J, & Sneddon, L G. Reactions of nido-6-SB[sub 9]H[sub 11] with imines. Structural characterization of endo-9-((t-Bu)MeC=NH)-arachno-6-SB[sub 9]H[sub 11]. United States. doi:10.1021/ic00050a006.
Kuepper, S, Carroll, P J, and Sneddon, L G. Wed . "Reactions of nido-6-SB[sub 9]H[sub 11] with imines. Structural characterization of endo-9-((t-Bu)MeC=NH)-arachno-6-SB[sub 9]H[sub 11]". United States. doi:10.1021/ic00050a006.
@article{osti_7186879,
title = {Reactions of nido-6-SB[sub 9]H[sub 11] with imines. Structural characterization of endo-9-((t-Bu)MeC=NH)-arachno-6-SB[sub 9]H[sub 11]},
author = {Kuepper, S and Carroll, P J and Sneddon, L G},
abstractNote = {The reaction of nido-6-SB[sub 9]H[sub 11] with N-tert-butylformaldimine results in the formation of the unique zwitterionic compound 9-((t-Bu)NH[sub 2][sup +]CH[sub 2])-nido-6-SB[sub 9]H[sub 9][sup [minus]] (1). The formation of 1 is consistent with a reaction sequence involving hydroboration of the imine at the B9 cage position accompanied by transfer of a proton from a cage-bridging site to the nitrogen atom. When 1 is then reacted with acetonitrile, a rearrangement occurs and the adduct exo-9-(CH[sub 3]CN)-endo-9-((t-Bu)NHCH[sub 2])-arachno-6-SB[sub 9]H[sub 10] (2) is formed. The reaction of nido-6-SB[sub 9]H[sub 11] with tert-butylmethylketimine (4) gives the substituted imine product endo-9-((t-Bu)MeC=NH)-arachno-6-SB[sub 9]H[sub 11] (6). A single-crystal x-ray study of 6 confirmed that the imine adopts an endo position with regard to the arachno-6-SB[sub 9]H[sub 11] framework. Furthermore, the observed imine hydrogen to cage sulfur distance (2.712 (28) [angstrom]) is less than the sum of the van der Waals radii of hydrogen and sulfur, suggesting that the observed endo configuration may be stabilized by N-H---S hydrogen-bonding interactions. Thermolysis of 6 results in hydrogenation and rearrangement of the imine group to produce exo-9-((t-Bu)MeC(H)NH[sub 2])-arachno-6-SB[sub 9]H[sub 11] (7).},
doi = {10.1021/ic00050a006},
journal = {Inorganic Chemistry; (United States)},
issn = {0020-1669},
number = ,
volume = 31:24,
place = {United States},
year = {1992},
month = {11}
}