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]

Journal Article · Wed Nov 25 04:00:00 EST 1992 · Inorganic Chemistry; (United States)

DOI:https://doi.org/10.1021/ic00050a006· OSTI ID:7186879

Kuepper, S; Carroll, P J; Sneddon, L G ^[1]

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1. Univ. of Pennsylvania, Philadelphia (United States)

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).

• OSTI ID: 7186879
• Journal Information: Inorganic Chemistry; (United States), Journal Name: Inorganic Chemistry; (United States) Vol. 31:24; ISSN 0020-1669; ISSN INOCAJ
• Country of Publication: United States
• Language: English

Related Subjects

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY
400201* -- Chemical & Physicochemical Properties
BORON COMPOUNDS
BORON HYDRIDES
CHEMICAL REACTIONS
COHERENT SCATTERING
CRYSTAL STRUCTURE
DATA
DIFFRACTION
EXPERIMENTAL DATA
HYDRIDES
HYDROGEN COMPOUNDS
IMINES
INFORMATION
MOLECULAR STRUCTURE
NUMERICAL DATA
ORGANIC COMPOUNDS
ORGANIC NITROGEN COMPOUNDS
SCATTERING
THERMAL DEGRADATION
X-RAY DIFFRACTION