Boron-11 nuclear magnetic resonance shift assignments for 8-iodo-1,2-dicarbadodecaborane(12) and related compounds

Aufderheide, Brian E.; Sprecher, Richard F.

doi:10.1021/ic50139a053

Cited by 12 publications

(6 citation statements)

References 5 publications

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“…Furthermore, comparison of the g factors for mono- and disubstituted compounds in Figure clearly suggests that the sensitivity in all unsubstituted sites of the o -carborane cage approximately doubles after introducing one more substituent, in agreement with earlier proposed shift additivity rules. ,− It is also obvious that the resulting A( 13 C and 1 H) effects in the disubstituted series derive from the combined A + β effect in the C1,2 vertexes. In addition, the shift diagrams can be used for accurate predictions of NMR shifts for all nuclei involved (see the dotted lines for the elusive 9,12-F 2 derivative and the predicted spectrum in Figures and S1).…”

Section: Resultssupporting

confidence: 83%

Quantitative Assessment of Substitution NMR Effects in the Model Series of o-Carborane Derivatives: α-Shift Correlation Method

2017

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The principles of a new α-shift correlation (ASC) NMR method are demonstrated on a model series of substituted derivatives of o-carborane for which reliable NMR data are available. This graphical method revealed an acceptable linear correlation between α(B) or α(C) shifts and those induced by substituents in unsubstituted (u) positions of the carborane cluster. The linearity holds for all nuclei involved in skeletal bonding: Δδ(N) = g × α (where N = B,C, and H). The factor g (slope of the correlation line × 10) becomes an important measure of sensitivity of a given cage position to substituent changes. The β, γ, and δ = A (= antipodal) shifts can be therefore derived from the α-shift, are linearly proportional, and reflect additive character in double substitution. The ASC method appears to be an important tool for quantitative assessment of substituent NMR effects in all exo-substituted boron-cluster systems.

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Section: Resultssupporting

confidence: 83%

Quantitative Assessment of Substitution NMR Effects in the Model Series of o-Carborane Derivatives: α-Shift Correlation Method

2017

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“…A different synthetic strategy was developed in a paper dedicated to the NMR study of 8-iodo-1,2-dicarba- closo -dodecaborane . The authors prepared 1-methoxycarbonyl-8-iodo-1,2-dicarba- closo -dodecaborane ( 9 , Scheme ) starting from the acetonitrile adduct of 2-iododecaborane ( 8 ) and methyl propiolate.…”

Section: Resultsmentioning

confidence: 99%

“…Regardless of such extensive study, one particular iodinated carborane, 8-iodo-1,2-dicarba- closo -dodecaborane, has never attracted chemists’ attention, even though its spectra were published (without synthetic details) as early as 1974 . Unlike other iodocarboranes, which can be conveniently prepared in one or two steps starting from ortho -carborane, 8-iodo-1,2-dicarba- closo -dodecaborane can only be prepared selectively (as a main product of the reaction, not as one of several possible halogenation or rearrangement isomers) from decaborane.…”

Section: Introductionmentioning

confidence: 99%

Unfairly Forgotten Member of the Iodocarborane Family: Synthesis and Structural Characterization of 8-Iodo-1,2-dicarba-closo-dodecaborane, Its Precursors, and Derivatives.

et al. 2012

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8-Iodo-1,2-dicarba-closo-dodecaborane (7) was prepared in three steps starting from decaborane-14 with 20% overall yield. In the presence of nucleophiles, compound 7 undergoes selective removal of the boron vertex in the position para to the iodine substituent to form the anionic nido-carborane 1-iodo-7,8-dicarba-nido-undecaborate. Capping of the corresponding dicarbollide dianion with BI(3) led to formation of the new carborane, 3,10-diiodo-1,2-dicarba-closo-dodecaborane (15). The same dicarbollide dianion reacts with cobalt and nickel acetylacetonates in anhydrous tetrahydrofuran to form the corresponding bis(dicarbollide) complexes with excellent yields. All compounds were characterized by multinuclear NMR and high-resolution mass spectroscopy. Structures of 2-iododecaborane (2), 8-iodo-1,2-dicarba-closo-dodecaborane (7), 1-ethoxycarbonyl-8-iodo-1,2-dicarba-closo-dodecaborane (10), cesium 1-iodo-7,8-dicarba-nido-undecaborate (13), 3,10-diiodo-1,2-dicarba-closo-dodecaborane (15), and cesium 3,3'-commo-(10-iodo-1,2-dicarba-3-cobalta-closo-dodecaborane)-(10'-iodo-1',2'-dicarba-3'-cobalta-closo-dodecaborane) (16) were established by X-ray analysis of single crystals.

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“…Thus, (PPh3)(CO)IrD2Cl might be a reasonable candidate. A suitable scheme for deuterium exchange by this catalyst could be based on the following equilibria: However, since L2IrCl species are also active catalysts for deuterium exchange, an equally suitable scheme could be based on eq [16][17][18][19] with (PPh3)(CO)IrCl as the L2IrCl species. The evidence is insufficient for valid conclusions.…”

Section: Discussionmentioning

confidence: 99%

“…L2IrCl + D2 -L2IrD2Cl (16) L2IrD2Cl + BH ^L2IrBHD2Cl -L2IrHDCl + BD (17) L2IrCl + BH ^L2IrBHCl (18) L2IrBHCl + D2 ^L2IrBHD2Cl -L2IrBDCl + HD (19) The reaction in eq 18 has been observed in the absence of deuterium22 and the (L2IrHCl)C2BioHi 1 species used for systems 35 and 37 were prepared in this manner. Equation 19is an equilibrium similar to eq 6.…”

Section: Discussionmentioning

confidence: 99%

Deuterium exchange at terminal boron-hydrogen bonds catalyzed by certain transition metal complexes. A qualitative study of selectivity and mechanism

Hoel¹,

Talebinasab-Savari²,

Hawthorne³

1977

J. Am. Chem. Soc.

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Boron-11 nuclear magnetic resonance shift assignments for 8-iodo-1,2-dicarbadodecaborane(12) and related compounds

Cited by 12 publications

References 5 publications

Quantitative Assessment of Substitution NMR Effects in the Model Series of o-Carborane Derivatives: α-Shift Correlation Method

Quantitative Assessment of Substitution NMR Effects in the Model Series of o-Carborane Derivatives: α-Shift Correlation Method

Unfairly Forgotten Member of the Iodocarborane Family: Synthesis and Structural Characterization of 8-Iodo-1,2-dicarba-closo-dodecaborane, Its Precursors, and Derivatives.

Deuterium exchange at terminal boron-hydrogen bonds catalyzed by certain transition metal complexes. A qualitative study of selectivity and mechanism

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