A pentuply-bridging thiocarbonyl group: x-ray crystal structure of a salt of the 1-thio-2-phenyl-1,2-dicarbadodecaborate (12) anion, [LH]+[S(Ph)C2B10H10]− (L = 1,8-N,N,N1,N1-tetramethylnaphthalene diamine)

Exo-π-bonding to an ortho-carborane hypercarbon atom: systematic icosahedral cage distortions reflected in the structures of the fluoro-, hydroxy- and amino-carboranes, 1-X-2-Ph-1,2-C2B10H10 (X = F, OH or NH2) and related anions

“…3,5 It is apparent from these and our present studies that the stronger the exo--bond is at C1, the more shielded the antipodal B12…”

“…In 2-phenyl-ortho-carborane itself, PhCb o H (Fig 1(a), R = Ph, X = H), the hypercoordinated carbon ('hypercarbon' 6 ) atom C1 forms a single bond to the exohydrogen atom and bonds of lower order to the five neighbouring cage atoms (one carbon, four borons). As the order of the exo-C-X bond increases from one to two, we 3 shall show how the bond to the neighbouring cage carbon atom is particularly affected, 4,8 When the aryl planes are roughly perpendicular to the ipsoC-C1-C2 plane (as preferred sterically in diaryl derivatives) the skeletal C1-C2 distance is longer than for other ring orientations. Involvement in exo C1-Cipso dative -bonding from the aryl -system reduces the capacity of the appropriate tangential p AO on C1 for C1-C2 skeletal -bonding ( Fig.…”

“…Derivatives of phenyl-ortho-carborane were used in order to label the second carbon atom with a group whose influence was already understood; without such a label, CH/BH disorder problems can make X-ray structure determination difficult. Here, our work on PhCb o X systems (some aspects of which have appeared in preliminary accounts [1][2][3][4][5] ) is intended to provide a definitive account of the systematically more pronounced cage distortions that occur near the cage carbon atom C1 as exo C1-X -bonding builds up. In 2-phenyl-ortho-carborane itself, PhCb o H (Fig 1(a), R = Ph, X = H), the hypercoordinated carbon ('hypercarbon' 6 ) atom C1 forms a single bond to the exohydrogen atom and bonds of lower order to the five neighbouring cage atoms (one carbon, four borons).…”

Preparative and structural studies on sulfur-linked carborane icosahedra: 2-Phenyl-ortho-carboranyl-sulfur systems (2-Ph-1,2-C2B10H10)2X (X=S, S2 or SO), and ortho-carboran-di-yl systems (1,2-C2B10H10Y)2 (Y=S or SO)

“…9,10,11 Our own published work so far has concentrated on one-cage systems and here we extend our investigation to the effect on of one π-donating atom of connecting it ed to two ortho-carborane cages. We prepared systems (PhCb o ) 2 X (X = S(1), S 2 (2) or SO (3)) in which the second cage carbon atom bore a phenyl substituent, 10,12 choosing 2-phenyl-ortho-carborane derivatives because they generally form suitable crystals for X-ray crystallographic studies (over fifty such compounds have been structurally characterised).…”

Trends in ortho-carboranes 1-X-2-R-1,2-C2B10H10 (R=Ph, Me) bearing an exo-CN-bonded substituent group (X=NO, NNR′ or NHR′′)

“…followed by many related studies [2,3] on ortho-carboranes containing thiolato and phosphino groups. However, this area has only recently been documented systematically by experimental and computational studies on systems RCb o X and XCb o X in which X is a potential -donor such as NH 2 , OH, SH or anions derived therefrom by deprotonation [4,5].…”