Synthesis of the 1-hydroxy-closo-decaborate anion [1-B10H9OH]2−

Nucleophilicity of Oximes Based upon Addition to a Nitrilium closo-Decaborate Cluster

“…In addition, the amidoxime derivatives generate 3-substituted 5-ethyl-1,2,4-oxadiazoles detected in trace amounts by HRESI + -MS (f); the latter reaction between nitriles and amidoximes has been studied 21 by us earlier. Hydroxyguanidine derivatives (Ph 3 PCH 2 Ph)[1], (Ph 3 PCH 2 Ph) [4], (Ph 3 PCH 2 Ph) [9], and (Ph 3 PCH 2 Ph) [12] decompose in solutions at RT for approximately 2 weeks, giving a broad mixture of products, whereas aromatic ketoxime derivative (Ph 3 PCH 2 Ph) [8] in solutions at RT decomposes after 4 days. In the cases of (Ph 3 PCH 2 Ph)[2−3], (Ph 3 P-CH 2 Ph)[5−7], (Ph 3 PCH 2 Ph)[10−11], and (Ph 3 PCH 2 Ph)- [13−14], the hydrolysis in a MeOH/H 2 O (10/1, v/v) mixture completes after 4 h at 60 °C.…”

“…Ph 3 PCH 2 Ph)[8]. Yield: >99% (NMR).HRESI − -MS (m/z): 189.2168 ([M − Ph 2 CN] •− , calcd 189.2164), 369.2987 ([M] − , calcd 369.2984), 1092.7416 ([2 M + Ph 3 PCH 2 Ph] − , calcd 1092.7409).…”

Synthesis, Structural Analysis, and Functional Group Interconversion in the [closo‐B10H8‐1,10‐X2]2– (X = CN, [OCRNMe2]+, OCOR, and [OH2]+) Derivatives

“…The bis‐phenyliodonium 1f provides a convenient access to the previously unknown dihydroxy derivative 1h‐2H ; it is available in 4 steps from the parent dianion A and 40 % overall yield. The only previously reported [ closo ‐B 10 H 9 ‐1‐OH] 2– was obtained in 82 % yield by decomposition of monodinitrogen derivative [ closo ‐B 10 H 9 ‐1‐N 2 ] – in aqueous NaF, while the equatorial isomer [ closo ‐B 10 H 9 ‐2‐OH] 2– was easily prepared by alkaline hydrolysis of the formate or acetate ester . The readily available [ closo ‐B 10 H 9 ‐1‐IPh] – offers a potentially alternative route to the 1‐hydroxy derivative following the sequence described for 1h‐2H .…”

Boron

“…12 In a related study, the diazonium-closo-decaborate cluster, [B 10 H 9 N 2 ] À , has been shown to react with oxygen nucleophiles such as [OH] À and [OR] À (R ¼ Me, Et, i Pr, Ph) in high yielding reactions to form the hydroxyl and alkyloxy clusters [1-B 10 H 9 -OH] À and [1-B 10 H 9 -OR] À , 2, respectively. 13 The structure of the nido-undecaborate anion [B 11 H 14 ] À has been investigated in several compounds, using single crystal X-ray analysis, NMR spectroscopy and computational studies, in order to establish the position of the endo/bridging hydrides. 14 The closo-B 12 cluster anion, [B 12 H 11 NH 2 ] À , containing an exo-polyhedral -NH 2 group has been reacted with various aldehydes to form anionic Schiff-base compounds of the general form [B 12 H 11 -NQC(H)-C 6 H 4 -R] À (RQCN, CH 2Q CH 2 -C 6 H 4 CN, (CH 2Q CH 2 -C 6 H 4 ) 2 CN).…”

“…183 The molecular structure of trichloro(1H-imidazole)boron adduct, C 3 H 4 N 2 Á BCl 3 , has been determined and reported. 184 The first representatives of an unknown family of organoboron compounds, the ((perfluoroorgano) ethynyl)trifluoroborate salts K[R F CQCBF 3 ] (R F ¼ CF 3 , C 3 F 7 , (CF 3 ) 2 CF, C 6 F 13 , CF 3 -CFQCF, C 4 F 9 CFQCF, C 6 F 5 ), have been prepared and characterized by multinuclear NMR spectroscopy ( 11 B, 13 C, and 19 F) and reported. 185 The molecular structure of the halo-borane B 8 F 12 (25), has been determined by gas phase electron diffraction and computational methods, and shown to have a highly asymmetric form as observed in the solid state.…”