Chemistry of C-trimethylsilyl-substituted heterocarboranes. 11. Synthetic, spectroscopic, structural, and bonding studies on the sodium, sodium lithium, and dilithium complexed "carbons adjacent" nido-carborane anions [2-(SiMe3)-3-(R)-2,3-C2B4H6-n]n- (R = SiMe3, Me, H; n = 1, 2). High-yield conversion to 1,2-dicarba-closo-hexaborane(6) derivatives: precursors to carbons apart dianionic carborane ligands

The N‐Lithiation of 2,4,6‐Triphenylborazine

“…[17] In this complex, one Li cation sits on top of an open C 2 B 3 face while the second is bonded sidewise to a B-B bond. This lithium carboranate on reaction with YCl 3 produces the complex [Li(thf) 4 ]{(1-Cl-1-H 6 )-2,2Ј,3,3Ј(Me 3 Si) 4 -4,4Ј,5,5Ј-Li(thf)[1,1Ј-commo-Y(2,3-C 2 B 4 H 4 ) 2 ]} [18] where the Li cation of the yttriate coordinates to four B atoms (2 each per carborane unit) with Li-B distances of 2.31(4), 2.27(4), and 2.49(4) Å.…”

“…In the starting material the Li-B distances are Li1-B3 2.291(9), Li1-B4 2.371(9), and Li1-B5 2.237(10) Å. [17] 3 . [20] In this molecule the Li atoms bridge to basal adjacent C atoms but binds also to B atoms with distances ranging from 2.239(6) and 3.251(6) Å. Li-C bond lengths are somewhat longer at 2.247-2.456(6) Å.…”

Half-sandwich halolanthanacarboranes of the “carbons adjacent” C2B4-carborane ligand systems: important synthons for new polyhedral cage constructs

“…The reaction of the monosodium compound, nido-1-Na(THF)-2,3-(SiMe 3 ) 2 -2,3-C 2 B 4 H 5 (1) [11] with anhydrous LnX 3 in a molar ratio of 2:1, in dry THF at 65°C…”

Silyl group mediated linkage of closo-C2B10-cage to nido-C2B4-carborane: synthesis of the novel carborane ligand, 1-R-2-[5′-(SiMe2CH2)-2′,3′-(SiMe3)2-2′,3′-C2B4H5]-1,2-C2B10H10 (R=Me, Ph)

“…However, their elemental analyses and spectroscopic data are all consistent with the structures shown for these compounds in Scheme 1. The 1 H NMR spectra of all the three compounds show resonances in the d ¼ À1:82 to )1.20 ppm range, which are characteristic for the B-H-B bridge hydrogens of the smaller cage [8,9]. In addition, resonances for the hydrogens in the various alkyl and/or aryl Inorganic Chemistry Communications 6 (2003) 1344-1346 www.elsevier.com/locate/inoche groups (CH 3 , C 6 H 5 , Si-CH 3 and CH 2 ) were all found in their expected regions of the 1 H NMR spectra.…”

“…The reaction of the sodium salt of the [nido-2,3-(Si(CH 3 ) 3 ) 2 -2,3-C 2 B 4 H 5 ] À anion [8,9] with (chloromethyl)dimethylchlorosilane, in a 1:1 molar ratio in diethyl ether, followed by extraction and purification, produced a new unique-B ðcageÞ -substituted small cage carborane, nido-5-ClCH 2 Si(CH 3 ) 2 -2,3-(Si(CH 3 ) 3 ) 2 -2,3-C 2 B 4 H 5 (1) in 81% yield (Scheme 1) [10]. The reaction of 1 with the lithium salt of the [closo-1-R-1,2-C 2 B 10 H 10 ] À anion (R ¼ Me, Ph) in 1:1 molar ratio in diethyl ether, followed by extraction and purification, produced the novel silyl-bridged, mixed carborane species, 1-R-2-[5 0 -SiMe 2 CH 2 -2 0 ; 3 0 -(SiMe 3 ) 2 -2 0 ; 3 0 -C 2 B 4 H 5 ]-1,2-C 2 B 10 H 10 [R ¼ Me (2) and Ph (3)], in yields of 76% and 81%, respectively [11,12].…”