Syntheses and structural characterizations ofcloso and nido 10-vertex metallatricarbanonaboranes

Perez-Gavilan, Ariane; Carroll, Patrick J.; Sneddon, Larry G.

doi:10.1135/cccc2010055

Cited by 10 publications

(9 citation statements)

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“…Deboronation of the isoelectronic 1-Cp-2-Ph-closo-1,2,3,4-MC 3 B 7 H 9 (M = Ru, Fe) complexes by tetrabutylammonium fluoride to form 2-Cp-10-Ph-closo-2,1,6,10-MC 3 B 6 H 8 (M = Ru, Fe) has previously been observed. 27 The 11 B NMR spectra of 14 (Supporting Information, Figure S25 Fluoride induced deboronation of the 1-Cp-2-Ph-closo-1,2,3,4-MC 3 B 6 H 8 (M = Ru, Fe) complexes was proposed 27 to initially occur by nucleophilic attack at the electropositive boron (B8) located between C2 and C4, followed by rearrangement of the Ph−C group to the four-coordinate cage position away from the metal-bonding face. As indicated by the arrows in eq 12, a similar pathway involving attack by the alkyne at the positive B8 boron of 8, followed by deboronation and cage rearrangement, could lead to the formation of 14.…”

Section: ■ Introductionmentioning

confidence: 99%

Syntheses, Structural Characterizations, and Reactivity Studies of Half-Sandwich Cobalt, Rhodium, and Iridium Metallatricarbadecaboranyl Complexes

et al. 2015

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The syntheses and structural characterizations of the first extensive series of Group 9 (Co, Rh, and Ir) tricarbadecaboranyl halfsandwich complexes are reported. The carbonyl complexes 1,1-(CO) 2 -2-Ph-closo-1,2,3,4-MC 3 B 7 H 9 , M = Co (1), Rh (2), and 8,8,8-(CO) 3 -9-Phnido-8,7,9,10-IrC 3 B 7 H 9 (3) were obtained by the reactions of Li + (6-Phnido-5,6,9-C 3 B 7 H 9 ) − with Co(CO) 4 I, [Rh(CO) 2 Cl] 2 , and Ir(CO) 3 Cl, respectively. Further reactions of 1, 2, and 3 with 1,2-bis(diphenylphosphino)ethane (dppe) yielded the 1,1-dppe-2-Ph-closo-1,2,3,4-MC 3 B 7 H 9 , M = Co (4), Rh (5), and 8-CO-8,8-dppe-9-Ph-nido-8,7,9,10-IrC 3 B 7 H 9 (6) derivatives with their crystallographic determinations showing that 1 and 2 contain the η 6 -2-Ph-2,3,4-C 3 B 7 H 9 1− ligand with the metallatricarbadecaboranyl cluster fragments having closo-octadecahedral geometries, while 3 has a slipped-cage η 4 -9-Ph-7,9,10-C 3 B 7 H 9 1− coordination and a nido-cluster framework. The reaction of Li + (6-Ph-nido-5,6,9-C 3 B 7 H 9 ) − with [Rh(COD)Cl] 2 and [Ir(COD)Cl] 2 produced the COD coordinated complexes 1,1-COD-2-Ph-closo-1,2,3,4-MC 3 B 7 H 9 , M = Rh (7), Ir (8), with η 6 -2-Ph-2,3,4-C 3 B 7 H 9 1− ligands and closo-cluster structures. On the other hand, slipped-cage structures with η 4 -9-Ph-7,9,10-C 3 B 7 H 9 1− coordination were achieved by the reactions of 1, 3, or 8 with an excess of the stronger donor tert-butyl isocyanide to give 8,8,8-(CN t Bu) 3 -9-Ph-nido-8,7,9,10-MC 3 B 7 H 9 , M = Co (9), Ir (10), respectively, or by the reaction of 8 with 1 equiv of tert-butyl isocyanide to give 8,8-COD-8-CN t Bu-9-Ph-nido-8,7,9,10-IrC 3 B 7 H 9 (11). Upon the reaction of 1 with diphenylacetylene, both carbonyls were displaced with subsequent alkyne cyclization to form the tetraphenylcyclobutadienyl complex 1,1-(η 4 -C 4 Ph 4 )-2-Ph-closo-1,2,3,4-CoC 3 B 7 H 9 (12). The crystalline tetramethylcyclobutadienyl derivative 1,1-(η 4 -C 4 Me 4 )-2-Ph-closo-1,2,3,4-CoC 3 B 7 H 9 (13) was synthesized by the reaction of Li + (6-Ph-nido-5,6,9-C 3 B 7 H 9 ) − with (η 4 -C 4 Me 4 )Co(CO) 2 I, and its crystallographic determination confirmed the formation of a complex where a formal Co 3+ ion is sandwiched between η 4 -C 4 Me 4 2− and η 6 -2-Ph-2,3,4-C 3 B 7 H 9 1− ligands.In contrast to the reactions with diphenylacetylene, the reaction of 8 with 3-hexyne resulted in cage deboronation to produce 2,2-COD-10-Ph-closo-2,1,6,10-C 3 B 6 H 8 (14). Neither 7 nor 8 would undergo oxidativeaddition when treated with I 2 . Although 11 reacted with I 2 and perfluoro-1-iodohexane, oxidative-addition products were also not obtained, but instead, iodation of a cage boron occurred to produce 8,8-COD-1-CN t Bu-9-Ph-11-I-nido-8,7,9,10-IrC 3 B 7 H 8 (15).

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Section: ■ Introductionmentioning

confidence: 99%

Syntheses, Structural Characterizations, and Reactivity Studies of Half-Sandwich Cobalt, Rhodium, and Iridium Metallatricarbadecaboranyl Complexes

et al. 2015

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“…Complexes of types 3-5 represent the first examples of monoaryl substituted ferratricarbollides and there is no doubt that a broad area of the twelve-vertex aryl or alkyl substituted metallacarborane chemistry has been opened that parallels the work in the fields of eleven-and ten-vertex metallatricarbaborane chemistry [36][37][38][39][40][41][42]. The compounds reported in this study are cluster-boron analogues of ferrocene [43] and their extremely high stability predestines them for biological uses and as starting substrates for further metallacarborane syntheses, e. g., polyhedral expansion and contraction reactions [44].…”

Section: Discussionmentioning

confidence: 99%

Acyl chloride carbon insertion into dicarbaborane cages – new route to tricarbollide cages

Štı́br

2014

Pure and Applied Chemistry

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Reactions between the arachno-6,9-C 2 B 8 H 14 dicarbaborane and acyl chlorides, RCOCl, in the presence of amine bases in CH 2 Cl 2 , followed by acidification with conc. H 2 SO 4 at 0 °C, generate in high yields a series of neutral alkyl and aryl tricarbollides of structure 8-R-nido-7,8,9-C 3 B 8 H 11 (where R = alkyls and aryls). These skeletal alkylcarbonation (SAC) reactions are consistent with an aldol-type condensation between the RCO group and open-face dicarbaborane hydrogen atoms, which is associated with the insertion of the acyl chloride RC unit into the structure under elimination of three extra hydrogen atoms as H 2 O and HCl. The reactions thus result in an effective cross-coupling between R and the tricarbollide cage. High-temperature reactions between 8-Ar-nido-7,8,9-C 3 B 8 H 11 (where Ar = Ph, 1-C 10 H 7 , and 2-C 10 H 7 ) compounds and [CpFe(CO) 2 ] 2 produced the first types of monoaryl substituted twelve-vertex ferratricarbollide complexes of general constitution [1-(CpFe)-closo-ArC 3 B 8 H 10 ] with three different arrangements of cluster carbon vertexes. The Fe-complexation is accompanied by extensive rearrangement of the cluster carbon atoms over the twelve-vertex cage and the complexes isolated can be regarded as ferrocene analogues.

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“…The 10-vertex C 3 B 6 H 9 Re(CO) 3 system differs significantly from the previously studied related CpFeC 3 B 6 H 9 system. 42 Thus, for the C 3 B 6 H 9 Re(CO) 3 system, the two lowest energy structures have degree 6 vertices for the rhenium atom, whereas the lowest energy CpFeC 3 B 6 H 9 structure, which is found experimentally in CpFe(C 3 B 6 H 8 Ph) and (η 2,2 -1,5-C 8 H 12 )Ir-(C 3 B 6 H 8 Ph), 20,21 is a bicapped tetragonal antiprism corresponding to B6C3Re-5 (Figure 6). The lowest energy bicapped tetragonal antiprism C 3 B 6 H 9 Re(CO) 3 structure B6C3Re-3 lies 5.1 kcal/mol in energy above the lowest energy structure B6C3Re-3.…”

Section: Inorganic Chemistrymentioning

confidence: 92%

“…The most extensive studies of these systems were done with CpFeC 3 B 7 H 9 R and Fe(C 3 B 7 H 9 R) 2 derivatives that are direct analogues of ferrocenes. − However, similar 11-vertex metallatricarbaboranes with vanadium, niobium, manganese, ,, rhenium, ruthenium, osmium, cobalt, , rhodium, iridium, and nickel have also been synthesized and structurally characterized. The 11-vertex metallatricarbaboranes CpM(C 3 B 7 H 9 Ph) (M = Fe, Ru) can be deboronated to give the corresponding 10-vertex metallatricarbaboranes CpM(C 3 B 6 H 8 Ph) using [nBu 4 N]F in tetrahydrofuran . These 10-vertex metallatricarbaboranes have a central MC 3 B 6 bicapped square antiprism framework with two of the three carbon atoms at the degree 4 vertices and the third carbon atom adjacent to one of these carbon atoms and to the metal atom.…”

Section: Introductionmentioning

confidence: 99%

“…The 11-vertex metallatricarbaboranes CpM(C 3 B 7 H 9 Ph) (M = Fe, Ru) can be deboronated to give the corresponding 10-vertex metallatricarbaboranes CpM(C 3 B 6 H 8 Ph) using [nBu 4 N]F in tetrahydrofuran. 21 These 10-vertex metallatricarbaboranes have a central MC 3 B 6 bicapped square antiprism framework with two of the three carbon atoms at the degree 4 vertices and the third carbon atom adjacent to one of these carbon atoms and to the metal atom. A similar 10-vertex MC 3 B 6 bicapped square antiprism is found in the iridium complex (η 2,2 -1,5-C 8 H 12 )Ir-(C 3 B 6 H 8 Ph).…”

Section: Introductionmentioning

confidence: 99%

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Deviations from the Most Spherical Deltahedra in Rhenatricarbaboranes Having 2n + 2 Wadean Skeletal Electrons

2017

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Density functional theory studies on the rhenatricarbaboranes CBHRe(CO) (n = 7-12) show that the lowest energy polyhedra for n-vertex metallaboranes having 2n + 2 skeletal electrons and sufficiently dissimilar vertex atoms can deviate from the most spherical closo deltahedra predicted by application of the Wade-Mingos rules. Furthermore, the lowest energy structures of these rhenatricarbaboranes are found to avoid C-C edges and have carbon atoms located at degree 4 rather than degree 5 vertices. The lowest energy structures for the 7-vertex CBHRe(CO) system all have a central CBRe closo deltahedron, namely the pentagonal bipyramid with the rhenium atom at a degree 5 axial vertex and all three carbon atoms at degree 4 equatorial vertices. However, the lowest energy structure for the 8-vertex CBHRe(CO) is not the most spherical closo 8-vertex deltahedron, namely the bisdisphenoid, but instead a central CBRe hexagonal bipyramid with mutually nonadjacent degree 4 vertices for the carbon atoms. Similarly, the lowest energy 10-vertex CBHRe(CO) structures are derived from isocloso deltahedra having three degree 4 vertices for all three carbon atoms rather than from the most spherical 10-vertex closo deltahedron, namely the bicapped square antiprism with only two degree 4 vertices. However, for the 9-vertex CBHRe(CO) system, the most spherical closo deltahedron, namely the tricapped trigonal prism, has three mutually nonadjacent degree 4 vertices, which is ideal for the three carbon atoms and thus is the preferred deltahedron. The preferred deltahedron for the 11-vertex CBHRe(CO) remains the most spherical closo deltahedron despite having only two degree 4 vertices for the carbon atoms. Furthermore, the six lowest energy 12-vertex CBHRe(CO) structures are all based on the regular icosahedron generally favored in polyhedral borane chemistry despite its complete lack of degree 4 vertices for the carbon atoms.

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Syntheses and structural characterizations ofcloso and nido 10-vertex metallatricarbanonaboranes

Cited by 10 publications

References 65 publications

Syntheses, Structural Characterizations, and Reactivity Studies of Half-Sandwich Cobalt, Rhodium, and Iridium Metallatricarbadecaboranyl Complexes

Syntheses, Structural Characterizations, and Reactivity Studies of Half-Sandwich Cobalt, Rhodium, and Iridium Metallatricarbadecaboranyl Complexes

Acyl chloride carbon insertion into dicarbaborane cages – new route to tricarbollide cages

Deviations from the Most Spherical Deltahedra in Rhenatricarbaboranes Having 2n + 2 Wadean Skeletal Electrons

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