“…Therefore, it is reasonable to assume that a boat to boat inversion occurs in solution as observed in the 9,10-dihydro-9,10-distannaanthracene . The tin analogue of 11 has been reported by Zakharkin et al 4 X-ray cystal structure of 11 with 50% probability thermal ellipsoids depicted. Selected bond lengths (Å) and angles (deg): Ge(1)−C(3) 1.930(4), Ge(1)−C(4) 1.933(4), Ge(1)−C(1) 1.982(3), Ge(1)−C(2) 1.986(3), C(1)−Ge(1)−C(2) 110.90(12).…”
The 1,2-bis(chlorogermyl)- (1) and 1,2-bis(bromostannyl)carborane (2) have been prepared by the reaction of dilithio-o-carborane with Me(2)GeCl(2) and Me(2)SnBr(2), respectively. Compounds 1 and 2 are found to be good precursors for the synthesis of a variety of cyclization compounds. The Wurtz-type coupling reaction of 1 and 2 using sodium metal afforded the four-membered digerma compound 3 and five-membered tristanna compound 4, respectively. The salt elimination reactions of 1 and 2 using Li(2)N(t)Bu and Li(2)PC(6)H(5) afforded the cyclic products [structure: see text]. The 1,2-bis(dimethylgermyl)carborane 9 and 1,2-bis(dimethylstannyl)carborane 10 were prepared by the reaction of 1 and 2 with sodium cyanoborohydride. The reactions of 9 and 10 with Pd(PPh(3))(4) afforded the bis(germyl)palladium 12 and bis(stannyl)palladium 13 complexes, respectively.
“…Therefore, it is reasonable to assume that a boat to boat inversion occurs in solution as observed in the 9,10-dihydro-9,10-distannaanthracene . The tin analogue of 11 has been reported by Zakharkin et al 4 X-ray cystal structure of 11 with 50% probability thermal ellipsoids depicted. Selected bond lengths (Å) and angles (deg): Ge(1)−C(3) 1.930(4), Ge(1)−C(4) 1.933(4), Ge(1)−C(1) 1.982(3), Ge(1)−C(2) 1.986(3), C(1)−Ge(1)−C(2) 110.90(12).…”
The 1,2-bis(chlorogermyl)- (1) and 1,2-bis(bromostannyl)carborane (2) have been prepared by the reaction of dilithio-o-carborane with Me(2)GeCl(2) and Me(2)SnBr(2), respectively. Compounds 1 and 2 are found to be good precursors for the synthesis of a variety of cyclization compounds. The Wurtz-type coupling reaction of 1 and 2 using sodium metal afforded the four-membered digerma compound 3 and five-membered tristanna compound 4, respectively. The salt elimination reactions of 1 and 2 using Li(2)N(t)Bu and Li(2)PC(6)H(5) afforded the cyclic products [structure: see text]. The 1,2-bis(dimethylgermyl)carborane 9 and 1,2-bis(dimethylstannyl)carborane 10 were prepared by the reaction of 1 and 2 with sodium cyanoborohydride. The reactions of 9 and 10 with Pd(PPh(3))(4) afforded the bis(germyl)palladium 12 and bis(stannyl)palladium 13 complexes, respectively.
“…Searching for a reversible linear coupling of the acidic p -carboranyl termini on the model systems 3 and 4 , to avoid the uncontrolled cross-linking expected for 1 , we tried linking through Hg atoms. Coupling of p -carborane carbons through mercury is sturdy and resembles the long-known and recently much exploited mercury coupling of o -carboranes.…”
A synthetic approach to a two-dimensional grid polymer is proposed and the execution of initial steps is described. Pd-catalyzed coupling of (1,12-dicarba-closo-dodecaboran-1-yl)copper ( 10) with iodobenzene, mdiiodobenzene, and 1,3,5-triiodobenzene yielded the known 1,12-dicarba-closo-dodecaboran-1-ylbenzene (3) and the new m-bis(1,12-dicarba-closo-dodecaboran-1-yl)benzene (4) and 1,3,5-tris(1,12-dicarba-closo-dodecaboran-1yl)benzene (1), respectively. Each arm of the trigonal connector 1 was provided with one or two sticky tentacles by conversion to 1,3,5-tris [12-((3-(ethylthio)propyl)dimethylsilyl)-1,12-dicarba-closo-dodecaboran-1-yl]benzene (7) and 1,3,5-tris [12-(bis(3-(ethylthio)propyl)methylsilyl)-1,12-dicarba-closo-dodecaboran-1-yl]benzene (8). Linear coupling of carboranyl CH terminals through a mercury atom produced very stable dimeric structures from 3 and 4. The carborane 3, its mercury-linked dimer 13, the 1:1 complex of 13 with 2,2′-bipyridyl, and the 2:1 complex of 13 with 2,2′-bipyrimidyl have been structurally characterized by single-crystal X-ray crystallography, but crystals of 1 showed an intriguing disorder and could not be used for molecular structure determination. Grazing incidence IR spectra show that the tentacled species 7 and 8 adsorb firmly on the surface of gold, apparently without a strong preference for a particular orientation. At room temperature, the tritentacled species 7 can be removed readily and the hexatentacled species 8 more slowly by treatment with a THF solution containing fluoride, which severs the tentacles.
“…The carborane substituents in 2 are distorted icosahedra with no particularly unusual bond distances or angles. The carborane C-C distance is 1.635(5) Å, whereas the average B-C distance is 1.696(20) Å, ranging from 1.658 (8) to 1.714 (7) Å. The average B-B bond distance for compound 2 is 1.769(16) Å, ranging from 1.731 (7) to 1.792(8) Å, whereas the C(1)-C(1′) distance is 1.519(4) Å.…”
Sterically hindered phosphine and arsine ligands derived from ortho-carborane were synthesized and characterized by X-ray crystallography. Tris(1'-methyl(1,2-dicarba-closo-dodecaboran-1-yl))phosphine, 2 (crystal data, hexagonal, space group P6(3), a = b = 12.251(3) A, c = 11.514(4) A, alpha = beta = 90 degrees, gamma = 120 degrees, V = 1496.6(7) A(3), Z = 2, R(1) = 0.0568) and tris(1'-methyl(1,2-dicarba-closo-dodecaboran-1-yl))arsine, 3 (crystal data, hexagonal, space group P6(3), a = b = 12.330(3) A, c = 11.474(4) A, alpha = beta = 90 degrees, gamma = 120 degrees, V = 1510.7(7) A(3), Z = 2, R(1) = 0.0930) were prepared in 82% and 68% yield, respectively. The phosphine ligand is resistant to air-oxidation but was converted to corresponding oxide when heated with hydrogen peroxide. The tertiary carboranyl phosphine reacted with (Tht)AuCl to yield chloro(tris(1'-methyl(1,2-dicarba-closo-dodecaboran-1-yl))phosphine)gold(I), 4 (crystal data, monoclinic, space group P2(1)/c, a = 19.101(4) A, b = 12.167(2) A, c = 13.846(3) A, alpha = gamma = 90 degrees, beta = 91.13(3) degrees, V = 3217.2(11) A(3), Z = 4, R(1) = 0.0396) in 82% yield. From the X-ray structure of the gold complex, the cone angle of the phosphine was determined to be 213(2) degrees, which is among the largest values reported to date.
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