Steric Effects in Heteroboranes. III. 1-Ph-2-Me-1,2-closo-C2B10H10

McGrath, Thomas D.; Welch, Alan J.

doi:10.1107/s0108270194005809

Cited by 15 publications

(2 citation statements)

References 3 publications

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“…Thus, in derivatives 1-Ph-2-X-1,2- closo -C 2 B 10 H 10 (X = Me, Br), the 2-substituent is sufficiently bulky to ensure a conformation near θ‘ = 0° (experimentally 16.7 and 2.2°, respectively) 2e,3c and results in C(1)-C(2) distances of 1.695(5) Å and 1.692(8) Å. Bulkier X groups, such as Ph,2a CCCPh,2e SiMe 3 ,3d and SiMe 2 t Bu 3e maintain or extend C(1)−C(2) and can additionally result in bending back of substituents and/or deformation of the cage.…”

Section: Discussionmentioning

confidence: 99%

“…Surprisingly, however, even though it can be regarded as the fusion of two fragments (phenyl and closo -carborane) each of which has an extensive chemistry, relatively little work on it or its derivatives has since been published. There are a few reports of derivatives of 1-Ph-2-X-1,2- closo -C 2 B 10 H 10 , where X is an organic group, an inorganic group, or a transition metal fragment; also, monophenylcarborane is readily deboronated [losing B(3) or B(6)] to afford the anion [7-Ph-7,8- nido -C 2 B 9 H 10 ] 2- which can function as an η-ligand to a variety of metal-based fragments …”

Section: Introductionmentioning

confidence: 99%

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1-Phenyl-1,2-dicarba-closo-dodecaborane, 1-Ph-1,2-closo-C₂B₁₀H₁₁. Synthesis, Characterization, and Structure As Determined in the Gas Phase by Electron Diffraction, in the Crystalline Phase at 199 K by X-ray Diffraction, and by ab Initio Computations

Brain¹,

Cowie²,

Donohoe³

et al. 1996

Inorg. Chem.

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The compound 1-phenyl-1,2-dicarba-closo-dodecaborane(12), 1-C(6)H(5)-1,2-closo-C(2)B(10)H(11) (1), has been synthesized and characterized by a complete assignment of its (11)B NMR spectrum via (11)B{(1)H}/(11)B{(1)H} (COSY), (1)H{(11)B(selective)} and (1)H{(11)B}/(1)H{(11)B} (COSY) spectroscopy. An electron- and X-ray diffraction investigation of 1, complemented by ab initio calculations, has been undertaken. The gas-phase electron-diffraction (GED) data can be fitted by several models describing conformations which differ in the position of the phenyl ring with respect to the carborane cage. Local symmetries ofC(2)(v)() and D(6)(h)() for the 1,2-C(2)B(10) and C(6) moieties, respectively, were adopted in the GED model in order to simplify the problem. In addition, constraints among the close-lying C-C and B-B bonds were employed. However, even though such simplifications led to satisfactory refinements (R(G) = 0.069-0.071), a unique, definitive solution could not be gained. The (C-C)(mean), (C-B)(mean) and (B-B)(mean) bond lengths,r(a), are ca. 1.44, 1.72, and 1.78 Å, respectively. The C(6) hexagon, with r(a)(C-C) = ca. 1.394 Å, either eclipses the C(1)-C(2) vector (overall C(s)() symmetry) or more or less eclipses the C(1)-B(4) cluster bond (overall C(1) symmetry). In contrast, in the solid at 199 K, the ring lies at a position intermediate between the two GED positions, as determined by X-ray crystallography [C(8)H(16)B(10), monoclinic P2(1)/a: a = 12.047(3) Å, b = 18.627(4) Å, c = 12.332(5) Å, beta = 110.09(4) degrees, Z = 8]. The C-B distances span the range 1.681(6)-1.743(5) Å, and B-B lengths lie between 1.756(6) and 1.795(6) Å. A similar conformation was found for the theoretical (RHF/6-31G level) structure which was fully optimized in C(1) symmetry. The r(e) distances are consistent with the dimensions derived in the experimental studies. IGLO calculations of the (11)B chemical shifts, in addition to SCF single-point energies of the GED structures, further support these observations.

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Section: Discussionmentioning

confidence: 99%

Section: Introductionmentioning

confidence: 99%

1-Phenyl-1,2-dicarba-closo-dodecaborane, 1-Ph-1,2-closo-C₂B₁₀H₁₁. Synthesis, Characterization, and Structure As Determined in the Gas Phase by Electron Diffraction, in the Crystalline Phase at 199 K by X-ray Diffraction, and by ab Initio Computations

Brain¹,

Cowie²,

Donohoe³

et al. 1996

Inorg. Chem.

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Luminescence Properties of C‐Diazaborolyl‐ortho‐Carboranes as Donor–Acceptor Systems

Weber

Kahlert

Brockhinke

et al. 2012

Chemistry A European J

162

132

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Seven derivatives of 1,2-dicarbadodecaborane (ortho-carborane, 1,2-C(2)B(10)H(12)) with a 1,3-diethyl- or 1,3-diphenyl-1,3,2-benzodiazaborolyl group on one cage carbon atom were synthesized and structurally characterized. Six of these compounds showed remarkable low-energy fluorescence emissions with large Stokes shifts of 15100-20260 cm(-1) and quantum yields (Φ(F)) of up to 65% in the solid state. The low-energy fluorescence emission, which was assigned to a charge-transfer (CT) transition between the cage and the heterocyclic unit, depended on the orientation (torsion angle, ψ) of the diazaborolyl group with respect to the cage C-C bond. In cyclohexane, two compounds exhibited very weak dual fluorescence emissions with Stokes shifts of 15660-18090 cm(-1) for the CT bands and 1960-5540 cm(-1) for the high-energy bands, which were assigned to local transitions within the benzodiazaborole units (local excitation, LE), whereas four compounds showed only CT bands with Φ(F) values between 8-32%. Two distinct excited singlet-state (S(1)) geometries, denoted S(1)(LE) and S(1)(CT), were observed computationally for the benzodiazaborolyl-ortho-carboranes, the population of which depended on their orientation (ψ). TD-DFT calculations on these excited state geometries were in accord with their CT and LE emissions. These C-diazaborolyl-ortho-carboranes were viewed as donor-acceptor systems with the diazaborolyl group as the donor and the ortho-carboranyl group as the acceptor.

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Polyhedral Carboranes

Fox

2007

Comprehensive Organometallic Chemistry III

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Steric Effects in Heteroboranes. III. 1-Ph-2-Me-1,2-closo-C2B10H10

Cited by 15 publications

References 3 publications

1-Phenyl-1,2-dicarba-closo-dodecaborane, 1-Ph-1,2-closo-C₂B₁₀H₁₁. Synthesis, Characterization, and Structure As Determined in the Gas Phase by Electron Diffraction, in the Crystalline Phase at 199 K by X-ray Diffraction, and by ab Initio Computations

1-Phenyl-1,2-dicarba-closo-dodecaborane, 1-Ph-1,2-closo-C₂B₁₀H₁₁. Synthesis, Characterization, and Structure As Determined in the Gas Phase by Electron Diffraction, in the Crystalline Phase at 199 K by X-ray Diffraction, and by ab Initio Computations

Luminescence Properties of C‐Diazaborolyl‐ortho‐Carboranes as Donor–Acceptor Systems

Polyhedral Carboranes

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Steric Effects in Heteroboranes. III. 1-Ph-2-Me-1,2-closo-C2B10H10

Cited by 15 publications

References 3 publications

1-Phenyl-1,2-dicarba-closo-dodecaborane, 1-Ph-1,2-closo-C2B10H11. Synthesis, Characterization, and Structure As Determined in the Gas Phase by Electron Diffraction, in the Crystalline Phase at 199 K by X-ray Diffraction, and by ab Initio Computations

1-Phenyl-1,2-dicarba-closo-dodecaborane, 1-Ph-1,2-closo-C2B10H11. Synthesis, Characterization, and Structure As Determined in the Gas Phase by Electron Diffraction, in the Crystalline Phase at 199 K by X-ray Diffraction, and by ab Initio Computations

Luminescence Properties of C‐Diazaborolyl‐ortho‐Carboranes as Donor–Acceptor Systems

Polyhedral Carboranes

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1-Phenyl-1,2-dicarba-closo-dodecaborane, 1-Ph-1,2-closo-C₂B₁₀H₁₁. Synthesis, Characterization, and Structure As Determined in the Gas Phase by Electron Diffraction, in the Crystalline Phase at 199 K by X-ray Diffraction, and by ab Initio Computations

1-Phenyl-1,2-dicarba-closo-dodecaborane, 1-Ph-1,2-closo-C₂B₁₀H₁₁. Synthesis, Characterization, and Structure As Determined in the Gas Phase by Electron Diffraction, in the Crystalline Phase at 199 K by X-ray Diffraction, and by ab Initio Computations