The first derivative of the methylium cation with the triple-decker substituent, [CpCo(C3B2Me5)RuC5Me4CH2]PF6 (2PF(6)), was synthesized from the reaction of the triple-decker complex CpCo(C3B2Me5)RuCp* (1) with the salt of the trityl cation [CPh3](+). The X-ray crystal structure of 2PF(6) reveals that the methylium carbon is bound to the ruthenium with Ru-C bond length of 2.259 angstrom and corresponds to the description of its structure as eta(6)-fulvene-ruthenium. Reactions of 2PF(6) with nucleophiles OH-, Ph3P, Et3N led to the corresponding derivatives of 1 in high yields. Aromatic amines PhNEt2 and 4-MeC6H4NH2 react with 2PF(6) to give the electrophilic aromatic substitution products quantitatively. Chemical reduction of 2PF(6) with Zn powder in tetrahydrofuran leads to the formation of the bis(triple-decker) derivative (CpCo(C3B2Me5)RuC5Me4CH2)(2) (10) with a CH2CH2-bridge. The structures of complexes 4, 7-10 were determined by X-ray diffraction. Density functional calculations support the crystallographically determined geometry of 2 and allow rationalization of some characteristics of its structure, spectroscopy, and reactivity.

The first derivative of the methylium cation with the triple-decker substituent, [CpCo(C3B2Me5)RuC5Me4CH2]PF6 (2PF6), was synthesized from the reaction of the tripledecker complex CpCo(C3B2Me5)RuCp* (1) with the salt of the trityl cation [CPh3] + . The X-ray crystal structure of 2PF6 reveals that the methylium carbon is bound to the ruthenium with Ru–C bond length 2.259 Å and corresponds to the description of its structure as η 6 -fulvene-ruthenium. Reactions of 2PF6 with nucleophiles OH – , Ph3P, Et3N led to the corresponding derivatives of 1 in high yields. Aromatic amines PhNEt2 and 4-MeC6H4NH2 react with 2PF6 to give the electrophilic aromatic substitution products quantitatively. Chemical reduction of 2PF6 with Zn powder in tetrahydrofuran leads to the formation of the bis(triple-decker) derivative (CpCo(C3B2Me5)RuC5Me4CH2)2 (10) with a CH2CH2-bridge. The structures of complexes 4, 5, 7–10 were determined by X-ray diffraction. Density functional calculations support the crystallographically determined geometry of 2 and allow rationalization of some characteristics of its structure, spectroscopy, and reactivity. 10.1002/chem.201702571 Chemistry A European Journal This article is protected by copyright. All rights reserved.

Homoleptic metal complexes of the boron heterocycle 2,3-dihydro-1,3-diborole f((RC)-C-1)(2)((RB)-B-2)(2)R-3(H)C} 1 are described. X-Ray crystal structure determinations of two nickel and platinum derivatives are presented. In the nickel complex [Ni(1d)(2)] 6d (R-1 = R-2 = R-3 = Et) the essentially coplanar heterocycles attain a pentahapto coordination mode with a gauche orientation with respect to one another. An 18 VE count is attained. In contrast, in the 14 VE platinum complex [Pt(1a)(2)] 4a (R-1 = R-2 = Et, R-3 = Me) the ligands are strongly folded and adopt a tetrahapto coordination. The molecule is centrosymmetric in the crystalline state. DFT MO calculations are presented to establish the relative stabilities of these coordination modes for nickel and platinum, respectively. (C) 2015 Elsevier B.V. All rights reserved.

Reaction of dilithio-o-carborane Li2C2B10H10 (generated in situ from o-carborane 1 and butyllithium) with the 1, 2-diborylbenzene derivative 1, 2-C6H4(iPr2NBCl)2 yielded the o-carborane compound 3 having the fused exo-polyhedral C2B2C2 heterocycle. The analogous reactions with 1, 1-bis(dimethylaminochloroboryl)ethane and with 1, 3-dichloro-1, 2,3-tris(dimethylamino)triborane(5) afforded the o-carborane compounds 5 and 7 containing the fused exo-polyhedral five-membered C2B2C and C2B3 rings, respectively. Attempts to use 1, 2-dichloro-1, 2-bis(dimethylamino)diborane(4) for the synthesis of the o-carborane compound 10 with a fused exo-polyhedral C2B2 ring instead led to the diborane(4)yl-o-carborane species 9c and 9d (the latter in trace amount), which contain a diborane(4)yl moiety bonded to the o-carborane. The molecular compositions of the new o-carborane derivatives follow from NMR spectroscopic and mass spectrometric data as well as from X-ray diffraction analyses of 3, 7 and 9c. The structures exhibit weak intramolecular C-H center dot center dot center dot H-B hydrogen-hydrogen interactions.

An entry from the Cambridge Structural Database, the world’s repository for small molecule crystal structures. The entry contains experimental data from a crystal diffraction study. The deposited dataset for this entry is freely available from the CCDC and typically includes 3D coordinates, cell parameters, space group, experimental conditions and quality measures.

für Naturforschung in cooperation with the Max Planck Society for the Advancement of Science under a Creative Commons Attribution 4.0 International License. Dieses Werk wurde im Jahr 2013 vom Verlag Zeitschrift für Naturforschung in Zusammenarbeit mit der Max-Planck-Gesellschaft zur Förderung der Wissenschaften e.V. digitalisiert und unter folgender Lizenz veröffentlicht: Creative Commons Namensnennung 4.0 Lizenz. Polydeckerkomplexe mit p, i;5-2,3-Dihydro-l,3-diborolylnickel-Fragmenten als Stapeleinheiten Polydecker Complexes with ,«,?75-2,3-Dihydro-l,3-diborolylnickel Fragments as Stacking Units

Reactions of dilithio-o-carborane Li2C2B10H10 (generated in situ from o-carborane 1 and butyllithium) with aminodichloroboranes R2NBCl2 (R = Et, iPr) led to the corresponding mono- and/or bis-C-amino-boryl-o-carboranes. The molecular compositions of the new o-carborane derivatives follow from NMR and MS data as well as from X-ray diffraction analyses. The structures of the new carborane compounds feature combined weak intramolecular C-H center dot center dot center dot H-B hydrogen-hydrogen and C-H center dot center dot center dot Cl hydrogen-chlorine bonding in the solid state. (C) 2013 Elsevier B. V. All rights reserved.

Cationic triple-decker complexes with a bridging diborolyl ligand, [CpCo(mu-1,3-C3B2Me5)M(ring)](+) (M-(ring) = CoCp (2a), CoCp* (2b), RhCp (3a), RhCp* (3b), IrCp (4a), IrCp* (4b), Ru(C6H6) (5a), Ru(p-MeC6H4Pri) (5b), Ru(C6Me6) (5c), Ru(eta(6)-cycloheptatriene) (6)), were synthesized by reaction of CpCo(mu-1,3-C3B2Me5)Tl with [M(ring)Hal(2))(2). The structures of 2aBPh(4), 2bPF(6), 4aPF(6), 5aOTf, and 5cPF(6) were determined by X-ray diffraction. The electron-transfer ability of the complexes has been ascertained by electrochemical and spectroelectrochemical techniques. In general, they are able to shuttle reversibly in the sequence 2+/+/0/-, plausibly affording completely delocalized mixed-valence derivatives. DFT calculations revealed structural changes accompanying redox processes and satisfactorily predicted the potentials for the first reduction and first oxidation.

The reaction of CpCo(1,3-C3B2Me5H) (1) with CpTl affords the thallium derivative CpCo(1,3-C3B2Me5)Tl (2). The structures of 1 and 2 were determined by X-ray diffraction at 100 K. An “extra” hydrogen atom in 1 occupies a C–H···B bridging position. According to DFT calculations, 1 exists as a mixture of two enantiomers with an enantiomerization barrier of only 0.5 kcal mol–1. The transition state has Cs symmetry with an endo-CH hydrogen atom. The isomeric iso-1with the Co–H···B bridge is less stable than 1 by 10 kcal mol–1.The formation of 1 and iso-1 from C3B2Me5H and CpCo(C2H4)2 have almost equal activation energies. The isomerization of iso-1 to 1 was shown to proceed as a two-step hydrogen transfer. The bonding of the “extra” hydrogen atom in the related CHB-bridged carborane nido-2,3,5-C3B3R5H2 and metallacarboranes M(C5R5)(C3B2R′5H) (R, R′ = H, Me; M = Co, Rh, Ir) as well as their hydridic isomers MH(C5R5)(C3B2R′5) was compared. According to energy decomposition analysis, the bonding of the parent anion [CpCo(1,3-C3B2H5)]– with metal cations becomes stronger in the following order: K+ < Na+ < Tl+ < Li+ < [RuCp]+. The attractive interactions between the [CpCo(1,3-C3B2H5)]– and Tl+ fragments are 68 % electrostatic and 32 % covalent.

The mu-diborolyl triple-decker complex CpCo(mu-1,3-C3B2Me5)PtMe3 was prepared by reaction of the sandwich anion [CpCo(1,3-C3B2Me5)](-) with [PtMe3I](4); according to energy decomposition analysis, attractive interactions between the [CpCo(1,3-C3B2Me5)](-) and [PtMe3](+) fragments are similar to 64% electrostatic and 36% covalent.

The reaction of closo-[B10H10]2− with [PtCl2(PPh3)2] in MeOH at reflux affords the B-methoxy substituted 11-vertex nido-platinaborane compound [(PPh3)2PtB10H10-8-H0.5(OCH3)0.5-10-(OCH3)] (1) and the known species [(PPh3)2PtB10H11-8-(OCH3)] (2) and 1,6-(PPh3)2B10H8 (3). The same reaction under solvothermal condition gives the partially degraded diplatinaborane [(PPh3)2(μ-PPh2)Pt2B9H7-3,9,11-(OMe)3] (4) with a novel nido-Pt2B9H10 skeleton. The new metallaborane compounds have been characterized by spectroscopic methods and single-crystal X-ray analyses. In particular, computational/theoretical chemistry supports the ultimate structural confirmation of 4. The structures of these metallaboranes exhibit interesting intra- and/or intermolecular C–H⋯O hydrogen bonding interactions.

The dimeric triple-decker type halides [CpCo(μ-1,3-C3B2Me5)MX2]2 (M = Rh, X = Cl, 1; M = Ir, X = Cl, 2; M = Rh, X = Br, 3; M = Ir, X = Br, 4) react with Me2SO and PPh3 giving adducts CpCo(μ-1,3-C3B2Me5)M(L)X2 (5–12). The Me2SO ligand is S-bonded to the metal atom in the solid state, while in acetone it is O-bonded. Structures of 5–12 were confirmed by X-ray diffraction.

The reaction of closo-B10H10 2− with PtCl2(PPh3)2 in the presence of MeCOSH afforded the title platinaborane nido-7,7-(PPh3)2-7-PtB10H11-11-OC(O)Me (1), which has been characterized by IR and NMR spectroscopy, MS, elemental analysis, and single-crystal X-ray diffraction. In contrast to the known products having exo-polyhedral Pt-S-C-O-B ring(s) from the same reaction with Ph- COSH, compound 1 has a B-acetoxy group on the open PtB4 face of the nido-PtB10 cluster. The structure of 1 features both intramolecular/intermolecular C-H· · ·O hydrogen bonds and intramolecular C-H· · ·H-B dihydrogen bonds, which link the molecules into a 1-D chain structure.

The reaction of closo-B10H102- with PtCl2(PPh3)(2) in the presence of MeCOSH afforded the title platinaborane nido-7,7-(PPh3)(2)-7-PtB10H11-11-OC(O)Me (1), which has been characterized by IR and NMR spectroscopy, MS, elemental analysis, and single-crystal X-ray diffraction. In contrast to the known products having exo-polyhedral Pt-S-C-O-B ring(s) from the same reaction with Ph-COSH, compound 1 has a B-acetoxy group on the open PtB4 face of the nido-PtB10 cluster. The structure of 1 features both intramolecular/intermolecular C-H center dot center dot center dot O hydrogen bonds and intramolecular C-H center dot center dot center dot H-B dihydrogen bonds, which link the molecules into a 1-D chain structure.

The paramagnetic triple-decker complexes [(Cp*Ru)(2){mu-(CMe)(3)(BCl)(BMe)}] (3b) and [(Cp*Ru)(2){mu-(CMe)(3)(BCl)(2)}] (3c) are formed by refluxing a mixture of [Cp*RuCl](4) and pentamethy1-2,3-dihydro-1,3-diborole in thf. In CH2Cl2 under air complex 3b slowly looses a hydrogen atom with formation of the diamagnetic triple-decker [(Cp*Ru)(2){mu-eta(5):eta(6)-(CMe)(3)-(BCl)(BCH2)}] (413) with the unsymmetrical dihydrodiborafulvene derivative in a bridging position. The analogous complex [(Cp*Ru)(2){mu-eta(5):eta(6)-(CMe)(3)(BMe)-(BCH2)]} (4a) is obtained by interaction of HCl with the triple-decker [(CP*Ru)(2)-{mu-(CMe)(3)(BMe)(2)}] (3a). According to calculations, complexes 4a and 4b have an almost non-distorted triple-decker arrangement with a strong bending of the B=CH2 group toward one of the Ru atoms. For the formation of 3b and 3c the chloro-containing sandwich complexes [Cp*Ru{eta(5)-(CMe)(3)-(BCl)(BR1)}] (2b,c R-1 = Me, Cl) are proposed as intermediates. The constitutions of the complexes are derived from NMR, MS and DFT data, and the molecular structure of 3b is confirmed by an X-ray diffraction analysis.

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AbstractThe cover picture shows the serendipitous transformation of the yellow into the dark orange triple‐decker sandwich complex by air. The unique B=CH2 group formed strongly leans toward one of the metal atoms. Non‐equivalence of the Cp*Ru groups suggests a bridge inversion, which does not occur below 70 °C. At higher temperatures the signals of the Cp* protons broaden, but coalescence is not reached in toluene. Details are discussed in the article by M. Enders, A. R. Kudinov, W. Siebert et al. on p. 2911 ff.

The cationic triple-decker complexes [CpCo(1,3-C3B2Me5)M(C5R5)](+) (M = Rh (2), Ir (3), R = H (a), Me (b)) with the bridging diborolyl ligand were synthesized by the reaction of the sandwich anion [CpCo(1,3-C3B2Me5)](-) (1) with the halide complexes [CpMI2](2) or [Cp*MCl2](2) (Cp* = C5Me5). The structures of [2b]PF6 and [3b]PF6 were established by X-ray diffraction. The nature of the metal-diborolyl bond in these complexes was analyzed using the energy decomposition scheme.

Triple-decker complexes with a bridging diborolyl ligand CpCo(μ-1,3-C3B2Me5)M(ring) (M(ring) = RuCp, 4; RuCp*, 5; Co(C4Me4), 6) were synthesized by electrophilic stacking of the sandwich anion [CpCo(1,3-C3B2Me5)]− with the [(ring)M(MeCN)3]+ cations. Structures of 4−6 were confirmed by X-ray diffraction. The electrochemical and spectroelectrochemical behavior of the complexes prepared was studied. DFT calculations of the redox potentials were also performed. Similar bonding properties of anions [CpCo(1,3-C3B2R5)]− and [C5R5]− (R = H, Me) toward [M(ring)]+ cations were established both experimentally (synthesis, electrochemistry, and X-ray diffraction) and theoretically (energy decomposition and Mulliken population analysis).