Quantum Chemistry Study on the Geometrical Structures of Small Centipedo－boranes

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Empirical and ab initio energy/architectural patterns for 73 nido-6<V>-carborane isomers, from B(6)H(9)(-) to C(4)B(2)H(6)

Qualitative rules governing carbon and bridge-hydrogen placement permit the prediction of the most stable isomeric structures for the various carboranes. Seventy-three isomeric boron hydride and carborane structures, from B(6)H(9)(-) to C(4)B(2)H(6), were computed at the ab initio MP2(fc)/6-31G level to determine their relative stabilities quantitatively. Specific architectural features, recognized to be unfavorable, were assigned "energy penalty" values that allow the projection of comprehensive thermodynamic stability values via a simple additivity procedure. These values match the ab initio results with surprising precision. Our study includes Siebert's nido-2,3,5-C(3)B(3)H(7) and Wrackmeyer's nido-2,4-C(2)B(4)H(8) nido-6 carboranes, which contain "unusual" CH-B-bridge hydrogens.     

Structure of 1-(arylselanyl)naphthalenes. 2. G dependence in 8-G-1-(p-YC(6)H(4)Se)C(10)H(6).

The structures of 8-G-1-(p-YC(6)H(4)Se)C(10)H(6) (1 (G = Cl) and 2 (G = Br): Y = H (a), OMe (b), Me (c), Cl (d), Br (e), COOEt (f), and NO(2) (g)) were investigated by X-ray crystallographic analysis, NMR spectroscopy, and ab initio MO calculations. The structures of all members in 1 and 2 are concluded to be type B, which is in striking contrast to the type A structure for 4d-g (4 (g(n)), where G = H). The Se-C(i) bond of the p-YC(6)H(4)Se group in 8-G-1-(p-YC(6)H(4)Se)C(10)H(6) is almost perpendicular to the naphthyl plane in type A, and it is located on the plane in type B. The chlorine and bromine substitution at the 8-position in 1 and 2 dramatically changes the type A structure of 4 (g(n)) to type B. The nonbonded G- - -Se-C 3c-4e type interaction must contribute to stabilize the type B structure. The type B structure in 1 and 2 should also be more stabilized than the same structure in 4 by the 3c-4e type interaction: The structure of 4b is type B in the crystals and type B would be more stable for 4c and might be for 4a in solutions. Ab initio MO calculations are performed on 8-G-1-(p-YC(6)H(4)Se)C(10)H(6), 8-G-C(10)H(6)SeH-1, and models HG- - -SeH(2), where G = Cl, Br, and F, to clarify the reason for the dramatic change in the structures. The type B structure is optimized to be more stable than the type A for all species examined, which supports the observations. The energy differences between type B and type A are larger for the models than for the naphthalenes. While the superiority of the type B for the former is Br > Cl > F, that of the latter is Br approximately Cl >/= F. These results show that the main factor of the structural change from type A to type B is the nonbonded G- - -Se-C 3c-4e interaction. The electronic effect of halogens through the naphthalene pi-framework would also contribute to some extent, although the direct comparison of the evaluated values between the naphthalene systems and the models is not so easy. Factors to stabilize the two structures of 1, 2, 4, and 8-(MeSe)-1-(p-YC(6)H(4)Se)C(10)H(6) are reexamined from a viewpoint of the nonbonded G- - -Se-C 3c-4e interaction (G dependence), together with the electronic effect of Y (Y dependence).     

Fluxional and aromatic behavior in small magic silicon clusters: a full ab initio study of Si(n), Si(n) (1-), Si(n) (2-), and Si(n) (1+), n=6, 10 clusters

The structural, electronic, vibrational, optical, magnetic, and aromatic characteristics of Si(n), Si(n) (1-), Si(n) (2-), and Si(n) (1+), clusters have been calculated very accurately with a variety of high level ab initio techniques. These calculations have been performed with the aim to clarify existing ambiguities in the literature and to bring up the fluxional and aromatic characteristics of these species. The fluxional behavior, according to earlier conjecture of the present author, could be connected to the magic property. In addition such behavior could also explain the existence of conflicting results. The ab initio techniques include quadratic configuration interaction, coupled cluster, and multireference second order perturbation theory, together with density functional theory ("static" and time dependent) with the hybrid B3LYP functional. Various high quality correlation-consistent basis sets, ranging from 2Z up to 5Z quality, were employed. It is demonstrated that Si(6) is fluxional, fluctuating around a symmetric D(4h) structure. Si(10) is also fluxional but to a lesser degree, in contrast to Si(10) (1-) anion which is highly fluxional. For both clusters, in full agreement with Wade's and Lipscomb's rules for deltahedral boranes, the corresponding dianions have higher symmetry (O(h) and D(4d), respectively) and lower energy than the neutral clusters. The aromatic behavior of Si(6) fits better to a mixed conflicting aromaticity picture. This type of aromatic and fluxional behavior has also been observed in stable "magic" carbon clusters as C(6) and carbon fullerenes such as C(20). The present results, which support possible connection of fluxional and magic properties, are in excellent agreement with experimental measurements of ionization energies, electron affinities, and vibrationally resolved photoelectron spectra.     

Photoelectron spectroscopy and ab initio study of the doubly antiaromatic B(6) (2-) dianion in the LiB(6) (-) cluster

A metal-boron mixed cluster LiB(6) (-) was produced and characterized by photoelectron spectroscopy and ab initio calculations. A number of electronic transitions were observed and used to compare with theoretical calculations. An extensive search for the global minimum of LiB(6) (-) was carried out via an ab initio genetic algorithm technique. The pyramidal C(2v) ((1)A(1)) molecule was found to be the most stable at all levels of theory. The nearest low-lying isomer was found to be a triplet C(2) ((3)B) structure, 9.2 kcal/mol higher in energy. Comparison of calculated detachment transitions from LiB(6) (-) and the experimental photoelectron spectra confirmed the C(2v) pyramidal global minimum structure. Natural population calculation revealed that LiB(6) (-) is a charge-transfer complex, Li(+)B(6) (2-), in which Li(+) and B(6) (2-) interact in a primarily ionic manner. Analyses of the molecular orbitals and chemical bonding of B(6) (2-) showed that the planar cluster is twofold (pi- and sigma-) antiaromatic, which can be viewed as the fusion of two aromatic B(3) (-) units.     

质子化硼烷正离子体系电子结构的理论研究

本文用a b initio计算法和近似a b initio计算法(PRDDO)研究了质子化硼烷正离子体系的电子结构,给出了一些正离子体系的优化几何构型并讨论了它们的成键情况。计算的硼烷分子质子亲和势与实验值相当吻合。     

Arachno, nido, and closo aromatic isomers of the Li6B6H6 molecule

We analyzed chemical bonding in low-lying isomers of the recently computationally predicted B(6)H(6)Li(6) molecule. According to our calculations the benzene-like B(6)H(6)Li(6) (D(2h), (1)A(1g)) arachno structure with the planar aromatic B(6)H(6)(6-) anion is the most stable one. A nido isomer with two aromatic B(6)H(6)(4-) (pentagonal pyramid) and Li(3)(+) (triangular) moieties, which can be considered as derived from the global minimum structure through a two-electron intramolecular transfer from B(6)H(6)(6-) to three Li(+) cations, was found to be 10.7 kcal/mol higher in energy. A closo isomer with three aromatic moieties (octahedral B(6)H(6)(2-) and two Li(3)(+)) was found to be 31.3 kcal/mol higher in energy than the global minimum. Another isomer with three aromatic moieties (two B(3)H(3)(2-) and Li(3)(+)) was found to be substantially higher in energy (74.4 kcal/mol). Thus, the intramolecular electron transfers from the highly charged B(6)H(6)(6-) anion to cations are not favorable for the B(6)H(6)Li(6) molecule, even when a formation of three-dimensional aromatic B(6)H(6)(2-) anion and two sigma-aromatic Li(3)(+) cations occurs in the closo isomer.     

Cyclopentadienyl ruthenium, rhodium, and iridium vertices in metallaboranes: geometry and chemical bonding

Most cyclopentadienylmetallaboranes containing the vertex units CpM (M = Co, Rh, Ir; Cp = eta(5)-cyclopentadienyl ring, mainly eta(5)-Me(5)C(5)) and CpRu donating two and one skeletal electrons, respectively, have structures closely related to binary boranes or borane anions. Smaller clusters of this type, such as metallaborane analogues of arachno-B(4)H(10) (e.g., (CpIr)(2)B(2)H(8)), nido-B(5)H(9) (e.g., (CpRh)(2)B(3)H(7) and (CpRu)(2)B(3)H(9)), arachno-B(5)H(11) (e.g., CpIrB(4)H(10)), B(6)H(6)(2)(-) (e.g., (CpCo)(4)B(2)H(4)), nido-B(6)H(10) (e.g., CpIrB(5)H(9) and (CpRu)(2)B(4)H(10)), and arachno-B(6)H(12) (e.g., (CpIr)(2)B(4)H(10)), have the same skeletal electron counts as those of the corresponding boranes. However, such clusters with eight or more vertices, such as metallaborane analogues of B(8)H(8)(2)(-) (e.g., (CpCo)(4)B(4)H(4)), arachno-B(8)H(14) (e.g., (CpRu)(2)B(6)H(12)), and nido-B(10)H(14) (e.g., (CpRu)(2)B(8)H(12)), have two skeletal electrons less than those of the corresponding metal-free boranes, analogous to the skeletal electron counts of isocloso boranes relative to those of metal-free deltahedral boranes. Some metallaboranes have structures not analogous to metal-free boranes but instead analogous to metal carbonyl clusters such as 3-capped square pyramidal (CpRu)(2)B(4)H(8) and (CpRu)(3)B(3)H(8) analogous to H(2)Os(6)(CO)(16) and capped octahedral (CpRh)(3)B(4)H(4) analogous to Os(7)(CO)(21). In the metallaborane structures closely related to metal-free boranes, the favored degrees of BH and CpM vertices appear to be 5 and 6, respectively.     

Molecular wheel B8(2-) as a new inorganic ligand. photoelectron spectroscopy and ab initio characterization of LiB8(-)

The bare B(8) cluster was previously reported to be a D(7h) molecular wheel with a triplet group state. The B(8)(2-) dianion was predicted to be a closed-shell singlet and double aromatic D(7h) molecular wheel. Here we report the experimental observation of B(8)(2-) stabilized by a Li(+) cation in LiB(8)(-) and its experimental characterization using photoelectron spectroscopy. Theoretical searches lead to a C(7v) LiB(8)(-) global minimum structure, and its calculated photodetachment transitions are in good agreement with the experimental values. Except for a small out-of-plane distortion due to the asymmetric Li(+) capping, the B(8)(2-) unit in LiB(8)(-) is nearly identical to the bare B(8)(2-), suggesting it is a robust and stable structural unit and may be used as a new ligand and building block in chemistry.     

Synthesis, structure, reactivity, and thermal isomerization of boron-substituted 13-vertex cobaltacarboranes (eta5-Cp)Co(eta6-R2C2B10Me8H2) (R = H, Et)

Reduction of boron-substituted carboranes o-R2C2B10Me8H2 (R = H, Et), thermal isomerization, and nucleophilic reaction of the resultant 13-vertex cobaltacarboranes were studied. Reaction of o-C2B10Me8H4 (1) with excess potassium metal in tetrahydrofuran (THF) gave, after recrystallization from a THF solution of 18-crown-6 ether, [[K(18-crown-6)(THF)2][K(18-crown-6)]][[4-(18-crown-6)-2,3,5,8,9,11,12,13-Me8-4,1,6-KC2B10H4]2] (2) in 78% yield. Interaction of 1 with excess sodium or potassium metal in THF, followed by treatment with CoCl2/CpNa and then aerobatic oxidation, afforded two boron-substituted 13-vertex cobaltacarboranes, 4-Cp-2,3,5,8,9,11,12,13-Me8-4,1,6-CoC2B10Me8H4 (3) and 4-Cp-2,3,5,9,10,11,12,13-Me8-4,1,6-CoC2B10Me8H4 (4), in 15% and 8% yield, respectively. Subsequently, thermal isomerization of 3 and 4 yielded another two new isomers, 4-Cp-2,3,5,6,8,11,12,13-Me8-4,1,9-CoC2B10Me8H4 (5) and 4-Cp-2,3,5,6,7,11,12,13-Me8-4,1,9-CoC2B10Me8H4 (6). Treatment of 3 or 4 with strong bases such as nBuLi and MeLi generated unexpected nucleophilic substitution products 4-nBuCp-2,3,5,8,9,11,12,13-Me8-4,1,6-CoC2B10Me8H4 (7), 4-nBuCp-2,3,5,9,10,11,12,13-Me8-4,1,6-CoC2B10Me8H4 (8a), and 4-MeCp-2,3,5,9,10,11,12,13-Me8-4,1,6-CoC2B10Me8H4 (8b) in good yields. Under the same reaction conditions, however, only one 13-vertex cobaltacarborane, 4-Cp-1,9-Et2-2,5,6,7,8,11,12,13-Me8-4,1,9-CoC2B10Me8H4 (10), was isolated when o-Et2C2B10Me8H2 (9) was used as the starting material. Complex 10 is a thermodynamically stable product and has a substitution pattern different from that of 3-6. These results show that the substituents on either the cage carbon or boron atoms have an important effect on the formation and thermal stability of the 13-vertex metallacarboranes. The formation of these complexes can be rationalized by the diamond-square-diamond mechanism.     

Structural diversity in solvated lithium aryloxides. Syntheses, characterization, and structures of [Li(OAr)(THF)x]n and [Li(OAr)(py)x]2 complexes where OAr = OC6H5, OC6H4(2-Me), OC6H3(2,6-(Me))2, OC6H4(2-Pr(i)), OC6H3(2,6-Pr(i)))2, OC6h4(2-Bu(t)), OC6H3(2,6-Bu(t)))2

A series of sterically varied aryl alcohols H-OAr [OAr = OC6H5 (OPh), OC6H4(2-Me) (oMP), OC6H3(2,6-(Me))2 (DMP), OC6H4(2-Pr(i)) (oPP), OC6H3(2,6-(Pr(i)))2 (DIP), OC6H4(2-Bu(t)) (oBP), OC6H3(2,6-(Bu(t)))2 (DBP); Me = CH3, Pr(i) = CHMe2, and Bu(t) = CMe3] were reacted with LiN(SiMe3)2 in a Lewis basic solvent [tetrahydrofuran (THF) or pyridine (py)] to generate the appropriate "Li(OAr)(solv)x". In the presence of THF, the OPh derivative was previously identified as the hexagonal prismatic complex [Li(OPh)(THF)]6; however, the structure isolated from the above route proved to be the tetranuclear species [Li(OPh)(THF)]4 (1). The other "Li(OAr)(THF)x" products isolated were characterized by single-crystal X-ray diffraction as [Li(OAr)(THF)]4 [OAr = oMP (2), DMP (3), oPP (4)], [Li(DIP)(THF)]3 (5), [Li(oBP)(THF)2]2, (6), and [Li(DBP)(THF)]2, (7). The tetranuclear species (1-4) consist of symmetric cubes of alternating tetrahedral Li and pyramidal O atoms, with terminal THF solvent molecules bound to each metal center. The trinuclear species 5 consists of a six-membered ring of alternating trigonal planar Li and bridging O atoms, with one THF solvent molecule bound to each metal center. Compound 6 possesses two Li atoms that adopt tetrahedral geometries involving two bridging oBP and two terminal THF ligands. The structure of 7 was identical to the previously reported [Li(DBP)(THF)]2 species, but different unit cell parameters were observed. Compound 7 varies from 6 in that only one solvent molecule is bound to each Li metal center of 7 because of the steric bulk of the DBP ligand. In contrast to the structurally diverse THF adducts, when py was used as the solvent, the appropriate "Li(OAr)(py)x" complexes were isolated as [Li(OAr)(py)2]2 (OAr = OPh (8), oMP (9), DMP (10), oPP (11), DIP (12), oBP (13)) and [Li(DBP)(py)]2 (14). Compounds 8-13 adopt a dinuclear, edge-shared tetrahedral complex. For 14, because of the steric crowding of the DBP ligand, only one py is coordinated, yielding a dinuclear fused trigonal planar arrangement. Two additional structure types were also characterized for the DIP ligand: [Li(DIP)(H-DIP)(py)]2 (12b) and [Li2(DIP)2(py)3] (12c). Multinuclear (6,7Li and 13C) solid-state MAS NMR spectroscopic studies indicate that the bulk powder possesses several Li environments for "transitional ligands" of the THF complexes; however, the py adducts possess only one Li environment, which is consistent with the solid-state structures. Solution NMR studies indicate that "transitional" compounds of the THF precursors display multiple species in solution whereas the py adducts display only one lithium environment.     

Stabilization of flat aromatic Si6 rings analogous to benzene: ab initio theoretical prediction

It is shown by ab initio calculations, based on density functional (DFT/B3LYP), and high level coupled-cluster [CCSD(T)] and quadratic CI [QCISD(T)] methods, that flat aromatic silicon structures analogous to benzene (C6H6) can be stabilized in the presence of lithium. The resulting planar Si6Li6 structure is both stable and aromatic, sharing many key characteristics with benzene. To facilitate possible synthesis and characterization of these species, routes of formation with high exothermicity are suggested and several spectral properties (including optical absorption, infrared, and Raman) are calculated.     

Carbon avoids hypercoordination in CB6(-), CB6(2-), and C2B5(-) planar carbon-boron clusters

The structures and bonding of CB6-, C2B5-, and CB62- are investigated by photoelectron spectroscopy and ab initio calculations. It is shown that the global minimum structures for these systems are distorted heptacyclic structures. The previously reported hexacyclic structures with a hypercoordinate central carbon atom are found to be significantly higher in energy and were not populated under current experimental conditions. The reasons why carbon avoids hypercoordination in these planar carbon-boron clusters are explained through detailed chemical-bonding analyses.     

Defective vertices in arachno borane networks

Triangulated boron networks can be described in terms of the deviation of their local vertex environments from the degree 5 vertices found in ideal icosahedra. Vertices of degrees other than 5 or equivalent are considered to be defective vertices. This method, which was previously applied to deltahedral borane anions B(n)H(n)(2-) and nido-B(n)H(n+4) boranes, has now been applied to arachno boranes of the types B(n)H(n+6) and B(n)H(n+5)(-) (4 < or = n < or = 10). The known structures of the neutral arachno boranes B(4)H(10), B(8)H(14), and n-B(9)H(15) consist of triangulated boron networks with no defective vertices in accord with their higher stabilities relative to other neutral arachno boranes. In other structures of known arachno boranes, there are relatively small numbers of defective vertices, and these are isolated as far as possible from each other.     

Synthesis and structures of selected benzamidinates of Li, Na, Al, Zr and Sn(II) using the C1-symmetric ligands [N(SiMe3)C(C6H4Me-4 or Ph)NPh]-

Several compounds based on the C(1)-symmetric ligands [N(R)C(Ar)NPh]- [abbreviated as B1 (Ar = C(6)H(4)Me-4) or B2 (Ar = Ph), R = SiMe(3)] are reported. They are the crystalline metal benzamidinates [Li(mu:kappa2-B1)(OEt2)](2) (1), [Al(kappa2-B1)2Me] (2), [Al(kappa2-B1)2X] [X = Cl/Me, 1 : 1 (3)], [Sn(kappa2-B1)2] (4), Zr(kappa2-B1)2Cl2 (5), [Zr(kappa2-B1)3Cl] (6), [Na(mu:kappa2-B1)(tmeda)]2 (7), K[B1] (8), Li(B2)(OEt2) (9) and Zr(kappa2-B1)3Cl (10) and the known benzamidine Z-H2NC(C6H4Me-4) = NPh (11). They were prepared by (i) insertion of the nitrile 4-MeC6H4CN (1, 7, 8, 11) or PhCN (9) into the appropriate M-N(R')Ph [R' = R and M = Li (1, 9), Na (7), K (8)] bond and subsequent hydrolysis for 11 [R' = H and M = Li], or (ii) a ligand transfer reaction using the lithium amidinate 1 and Al(Me)2Cl (2, 3), SnCl2 (4) or ZrCl4 (5, 6), or Li(B2) and ZrCl4 (10). The X-ray structures of 1, 2, 3, 4, 6b (i.e..3PhMe) 7, and 11 are presented. Exploratory polymerisation experiments are described, using 2, 5 or 6 as a procatalyst with methylaluminoxane (MAO) (Al : Zr ca. 500 : 1) as promoter. Thus toluene solutions were exposed to C2H4 under ambient conditions; while 2 was unresponsive, 5 and 6 showed modest activity in the formation of polyethylene.     

The structure of arachno-[B6H11]-, at -25 degrees C in (CD3)2O,is resolved via the ab initio/IGLO-GIAO/NMR procedure

The arachno-[B6H11]- solution structure at -25 degrees C was clarified as fluxional compound 2 by applying the ab initio/IGLO/NMR method. The anion 2 can be derived from arachno-B6H12, 1, by the removal of the B2/B3 bridging hydrogen (2). No minimum on the potential energy surface could be found for an asymmetric complex, a, between [B5H8]- and BH3, which had been proposed originally. A Cs-symmetric [mu-(BH3)B5H8]- complex, A, only 3.2 kcal mol-1 higher in energy than 2, is the intermediate in the fluxional rearrangement observed on the NMR time scale. The transition structure [D] connecting 2 (Erel = 0.0) and A (Erel = 3.2) has a relative energy of 9.7 kcal mol-1. The elimination of both a and A as "most stable structure" candidates of arachno-[B6H11]- reinforces the early geometrical bonding systematics for boranes and carboranes.     

Overcrowding motifs in large PAHs. An ab initio study.

Planar and overcrowded LPAHs C(34)H(18) anthra[9,1,2-cde]benzo[rst]penaphene (1), benzo[rst]phenanthro[10,1,2-cde]pentaphene (2), tetrabenzo[a,cd,j,lm]perylene (3), tetrabenzo[a,cd,lm,o]perylene (4), and LPAHs C(38)H(18) anthra[2,1,9,8-klmno]naphtho[3,2,1,8,7-vwxyz]hexaphene (5), dianthra[2,1,9,8-stuva;2',1',9',8'-hijkl]pentacene (6), dibenzo[jk,uv]dinaphtho[2,1,8,7-defg;2',1',8',7'-opqr]perylene (7), diphenanthro[5,4,3-abcd;3',4',5'-lmno]perylene (8), potential products of peri-peri reductive couplings of benzanthrone and of naphthanthrone, respectively, were subjected to an ab initio study with emphasis on overcrowding motifs. The HF and DFT B3LYP methods were employed to calculate energies and geometries of the minima conformations of these LPAHs. The most stable LPAHs in these series were found to be planar C(2)(v)()-1 and C(2)(v)()-5, respectively. Among overcrowded LPAHs, twisted-folded C(2)-3 and C(2)-7 with two cove regions were found to be more stable than their respective isomers twisted-folded C(2)-4 and C(2)-8 with one fjord region each, in contrast to the semiempirical predictions. The energy differences between the most stable planar isomer and the overcrowded isomers were significantly smaller in the C(38)H(18) series, than in the C(34)H(18) series. Overcrowded twisted-folded C(2)-7 with two coves was found to be more stable than planar C(2)(h)()-6 by 2.0 kJ/mol (at B3LYP/6-311G), indicating enhanced role of aromatic stabilization and decreased destabilization due to overcrowding, with increasing the number of aromatic rings. Heats of formation of LPAHs 1-8 were derived from the ab initio total energies (at B3LYP/6-31G). A search of the conformational spaces of 3 and 4 revealed an anti-folded local minimum C(i)()-3 and a syn-folded transition state C(s)()-4, 23.7 and 120.3 kJ/mol higher in energy than the twisted-folded C(2)-3 and C(2)-4, respectively (at B3LYP/6-31G). The cove and fjord torsion angles in the C(38)H(18) series were found to be smaller than in the C(34)H(18) series. The nonbonding distances between carbon atoms at cove and fjord regions of the overcrowded LPAHs were found to be smaller than the sum of the van der Waals radii of two carbon atoms     

Separating electrophilicity and Lewis acidity: the synthesis, characterization, and electrochemistry of the electron deficient tris(aryl)boranes B(C6F5)(3-n)(C6Cl5)n (n = 1-3)

A new family of electron-deficient tris(aryl)boranes, B(C(6)F(5))(3-n)(C(6)Cl(5))(n) (n = 1-3), has been synthesized, permitting an investigation into the steric and electronic effects resulting from the gradual replacement of C(6)F(5) with C(6)Cl(5) ligands. B(C(6)F(5))(2)(C(6)Cl(5)) (3) is accessed via C(6)Cl(5)BBr(2), itself prepared from donor-free Zn(C(6)Cl(5))(2) and BBr(3). Reaction of C(6)Cl(5)Li with BCl(3) in a Et(2)O/hexane slurry selectively produced B(C(6)Cl(5))(2)Cl, which undergoes B-Cl exchange with CuC(6)F(5) to afford B(C(6)F(5))(C(6)Cl(5))(2) (5). While 3 forms a complex with H(2)O, which can be rapidly removed under vacuum or in the presence of molecular sieves, B(C(6)Cl(5))(3) (6) is completely stable to refluxing toluene/H(2)O for several days. Compounds 3, 5, and 6 have been structurally characterized using single crystal X-ray diffraction and represent the first structure determinations for compounds featuring B-C(6)Cl(5) bonds; each exhibits a trigonal planar geometry about B, despite having different ligand sets. The spectroscopic characterization using (11)B, (19)F, and (13)C NMR indicates that the boron center becomes more electron-deficient as n increases. Optimized structures of B(C(6)F(5))(3-n)(C(6)Cl(5))(n) (n = 0-3) using density functional theory (B3LYP/TZVP) are all fully consistent with the experimental structural data. Computed (11)B shielding constants also replicate the experimental trend almost quantitatively, and the computed natural charges on the boron center increase in the order n = 0 (0.81) < n = 1 (0.89) < n = 2 (1.02) < n = 3 (1.16), supporting the hypothesis that electrophilicity increases concomitantly with substitution of C(6)F(5) for C(6)Cl(5). The direct solution cyclic voltammetry of B(C(6)F(5))(3) has been obtained for the first time and electrochemical measurements upon the entire series B(C(6)F(5))(3-n)(C(6)Cl(5))(n) (n = 0-3) corroborate the spectroscopic data, revealing C(6)Cl(5) to be a more electron-withdrawing group than C(6)F(5), with a ca. +200 mV shift observed in the reduction potential per C(6)F(5) group replaced. Conversely, use of the Guttmann-Beckett and Childs' methods to determine Lewis acidity on B(C(6)F(5))(3), 3, and 5 showed this property to diminish with increasing C(6)Cl(5) content, which is attributed to the steric effects of the bulky C(6)Cl(5) substituents. This conflict is ascribed to the minimal structural reorganization in the radical anions upon reduction during cyclic voltammetric experiments. Reduction of 6 using Na((s)) in THF results in a vivid blue paramagnetic solution of Na(+) [6](?-); the EPR signal of Na(+)[6](?-) is centered at g = 2.002 with a((11)B) 10G. Measurements of the exponential decay of the EPR signal (298 K) reveal [6](?-) to be considerably more stable than its perfluoro analogue.     

Heavy-metal aromatic and conjugated species: rings, oligomers, and chains of tin in Li(9)(-)(x)EuSn(6+)(x), Li(9)(-)(x)CaSn(6+)(x), Li(5)Ca(7)Sn(11), Li(6)Eu(5)Sn(9), LiMgEu(2)Sn(3), and LiMgSr(2)Sn(3)

The title compounds were synthesized from the elements by heating the corresponding mixtures at high temperature. Their structures were determined from single-crystal X-ray diffraction. Li(9)(-)(x)()EuSn(6+)(x)(), Li(9)(-)(x)()CaSn(6+)(x)(), Li(5)Ca(7)Sn(11), and Li(6)Eu(5)Sn(9) contain columns of stacked aromatic pentagons of Sn(5)(6)(-) that are analogous to the cyclopentadienyl anion C(5)H(5)(-). The pentagons are separated with Ca(2+) or Eu(2+) in the columns and resemble a polymeric metallocene. In addition to the columns, the isostructural Li(9)(-)(x)()EuSn(6+)(x)() and Li(9)(-)(x)()CaSn(6+)(x)() contain isolated tin atoms and bent tin trimers while Li(5)Ca(7)Sn(11) and Li(6)Eu(5)Sn(9) contain flat zigzag hexamers and flat zigzag infinite chains of tin, respectively. The isostructural LiMgEu(2)Sn(3) and LiMgSr(2)Sn(3) do not contain columns of pentagons but only flat zigzag infinite chains of tin. The aromaticity of the pentagons and the conjugation of the pi-systems of the hexamers and the infinite chains are discussed. The title compounds are also characterized by magnetic and conductivity measurements.     

Valence isoelectronic substitution in the B8(-) and B9(-) molecular wheels by an Al dopant atom: umbrella-like structures of AlB7(-) and AlB8(-)

The structures and the electronic properties of two aluminum-doped boron clusters, AlB(7)(-) and AlB(8)(-), were investigated using photoelectron spectroscopy and ab initio calculations. The photoelectron spectra of AlB(7)(-) and AlB(8)(-) are both broad, suggesting significant geometry changes between the ground states of the anions and the neutrals. Unbiased global minimum searches were carried out and the calculated vertical electron detachment energies were used to compare with the experimental data. We found that the Al atom does not simply replace a B atom in the parent B(8)(-) and B(9)(-) planar clusters in AlB(7)(-) and AlB(8)(-). Instead, the global minima of the two doped-clusters are of umbrella shapes, featuring an Al atom interacting ionically with a hexagonal and heptagonal pyramidal B(7) (C(6v)) and B(8) (C(7v)) fragment, respectively. These unique umbrella-type structures are understood on the basis of the special stability of the quasi-planar B(7)(3-) and planar B(8)(2-) molecular wheels derived from double aromaticity.