Predictive schemes for the reactivity of borane carbonyl and the stability of carbonyltrihydroborate anions, BH3C(O)X−

Spielvogel, Bernard F.; McPhail, Andrew T.; Knight, Jimmy A.; Moreland, Charles G.; Gatchell, Catherine L.; Morse, Karen W.

doi:10.1016/s0277-5387(00)84397-1

Cited by 18 publications

(6 citation statements)

References 24 publications

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“…Using boranes as the reducing reagents is desirable and potentially useful. [5,6] We have now found that B À H borane reduction of carbon monoxide can be carried out with a suitable borane at a frustrated phosphane/borane Lewis pair (FLP) [7,8] template. H. C. Brown had shown that R 3 B systems readily react with CO at 100 to 125 8C at normal pressure to yield the respective tertiary alcohols after oxidative workup.…”

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confidence: 99%

“…À64 8C) that dissociates at atmospheric pressure. [5,6] We have now found that B À H borane reduction of carbon monoxide can be carried out with a suitable borane at a frustrated phosphane/borane Lewis pair (FLP) [7,8] template. We stirred a mixture of the bulky cyclopentenylphosphane 1 with the hydroboration reagent [HB(C 6 F 5 ) 2 ] [9] for about 15 minutes at RT and then subjected the resulting mixture to an atmosphere of carbon monoxide (2 bar).…”

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confidence: 99%

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Facile Carbon Monoxide Reduction at Intramolecular Frustrated Phosphane/Borane Lewis Pair Templates

et al. 2013

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Facile Carbon Monoxide Reduction at Intramolecular Frustrated Phosphane/Borane Lewis Pair Templates

et al. 2013

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“…The [(CF 3 ) 3 BC(O)Hal] − anions are the first examples of mononuclear boron haloacyl derivatives. Early attempts to synthesize a chloroacyl complex of H 3 BCO by addition of chloride failed and instead yielded (MeBO) 3 23. A few examples of boron clusters that contain the chloroacyl substituent, for example, 9‐chloroacyl‐1,2‐dicarba‐ closo ‐dodecaborane, have been described24, 25 and their chemistry has been studied to some extent 24.…”

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confidence: 99%

Haloacyl Complexes of Boron, [(CF₃)₃BC(O)Hal]⁻(Hal=F, Cl, Br, I)

Finze

Bernhardt

Willner

et al. 2005

Chemistry A European J

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The haloacyltris(trifluoromethyl)borate anions [(CF3)3BC(O)Hal]- (Hal=F, Cl, Br, I) have been synthesized by reacting (CF3)3BCO with either MHal (M=K, Cs; Hal=F) in SO2 or MHal (M=[nBu4N]+, [Et4N]+, [Ph4P]+; Hal=Cl, Br, I) in dichloromethane. Metathesis reactions of the fluoroacyl complex with Me3SiHal (Hal=Cl, Br, I) led to the formation of its higher homologues. The thermal stabilities of the haloacyltris(trifluoromethyl)borates decrease from the fluorine to the iodine derivative. The chemical reactivities decrease in the same order as demonstrated by a series of selected reactions. The new [(CF3)3BC(O)Hal]- (Hal=F, Cl, Br) salts are used as starting materials in the syntheses of novel compounds that contain the (CF3)3B-C fragment. All borate anions [(CF3)3BC(O)Hal]- (Hal=F, Cl, Br, I) have been characterized by multinuclear NMR spectroscopy (11B, 13C, 17O, 19F) and vibrational spectroscopy. [PPh4][(CF3)3BC(O)Br] crystallizes in the monoclinic space group P2/c (no. 13) and the bond parameters are compared with those of (CF3)3BCO and K[(CF3)3BC(O)F]. The interpretation of the spectroscopic and structural data are supported by DFT calculations [B3LYP/6-311+G(d)].

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“…But only in the case of H 3 BCO have reactions with nucleophiles been studied. [63,[75][76][77][78] Similar to the reactions of (CF 3 ) 3 BCO, nucleophiles react with H 3 BCO either under addition or ligand exchange. In many cases the hydridic H atoms react with the primarily formed products; thus, the synthesis of H 3 B complexes is much more limited compared to the preparation of derivatives of (CF 3 ) 3 B.…”

Section: Reactions Of Trifluoromethyl Ligands At Boron With Lewis Andmentioning

confidence: 99%

“…In contrast, the borane carbonyl has a halflife of 45 min at 28 8C. [77] Hence, a comparison of the chemistry is not possible. However, the reactions described for [(CF 3 ) 3 BC(O)Hal] À (Hal = F, Cl, Br) are similar to reactions of chloro and fluoroacyl substituents of B atoms of o-, m-, and p-carboranes [82][83][84] as well as acid chlorides in organic chemistry.…”

Section: Halogenoacyltris(trifluoromethyl)boratesmentioning

confidence: 99%

Trifluoromethylboranes and ‐Borates: New Synthetic Strategies and Applications

2007

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The synthesis of salts with the [B(CF(3))(4)](-) anion has been the starting point for new developments in the field of trifluoromethylboron chemistry. In contrast to the previous syntheses of (CF(3))(n)B derivatives (n=1-3), achieved exclusively by CF(3) transfer, the synthesis of the [B(CF(3))(4)](-) anion was accomplished by fluorination of the [B(CN)(4)](-) anion with ClF or ClF(3) in anhydrous HF. Owing to its thermal and chemical stability, [B(CF(3))(4)](-) is an attractive weakly coordinating anion. However, in concentrated sulfuric acid one of the four CF(3) groups is solvolyzed to a CO ligand to yield the neutral borane carbonyl (CF(3))(3)BC[triple bond]O. It has been shown that the borane carbonyl compound is a versatile synthetic building block, and numerous reactions have been investigated. The addition of nucleophiles to the C atom of the CO ligand is favored, and examples for new derivatives are the anions [(CF(3))(3)BC[triple bond]Pnic](-) (Pnic=N, P, As). Under certain conditions, ligand-exchange reactions are also observed, for example, the formation of (CF(3))(3)BN[triple bond]CH. Finally, the borane carbonyl compound is a component of the conjugated Brønsted-Lewis superacid HF/(CF(3))(3)BCO.

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Predictive schemes for the reactivity of borane carbonyl and the stability of carbonyltrihydroborate anions, BH3C(O)X−

Cited by 18 publications

References 24 publications

Facile Carbon Monoxide Reduction at Intramolecular Frustrated Phosphane/Borane Lewis Pair Templates

Facile Carbon Monoxide Reduction at Intramolecular Frustrated Phosphane/Borane Lewis Pair Templates

Haloacyl Complexes of Boron, [(CF₃)₃BC(O)Hal]⁻(Hal=F, Cl, Br, I)

Trifluoromethylboranes and ‐Borates: New Synthetic Strategies and Applications

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Predictive schemes for the reactivity of borane carbonyl and the stability of carbonyltrihydroborate anions, BH3C(O)X−

Cited by 18 publications

References 24 publications

Facile Carbon Monoxide Reduction at Intramolecular Frustrated Phosphane/Borane Lewis Pair Templates

Facile Carbon Monoxide Reduction at Intramolecular Frustrated Phosphane/Borane Lewis Pair Templates

Haloacyl Complexes of Boron, [(CF3)3BC(O)Hal]−(Hal=F, Cl, Br, I)

Trifluoromethylboranes and ‐Borates: New Synthetic Strategies and Applications

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Haloacyl Complexes of Boron, [(CF₃)₃BC(O)Hal]⁻(Hal=F, Cl, Br, I)