Electrophilic reactions of protonated closo-B10H102- with arenes, alkane carbon-hydrogen bonds, and triflate ion forming aryl, alkyl, and triflate nido-6-X-B10H13 derivatives

Hawthorne, M. Frederick; Mavunkal, Ipe J.; Knobler, Carolyn B.

doi:10.1021/ja00037a074

Cited by 47 publications

(48 citation statements)

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“…[9] Now we have found that trans-M 2 [B 20 H 18 H 19 ] À ion, which is designated as fac-[B 20 H 19 ] À in the following discussion. It is known that under acidic conditions the closo-[B 10 H 10 ] 2À ion reacts to form nido-B 10 H 13 X, [25,26] nido-B 10 H 12 X 2 , [27,28] or BF 3 /[BF 4 ] À . [29][30][31] In view of these reactions, the rearrangement of trans-[B 20 H 18 ] 2À (Figure 1) might be initiated by protonation of one of its two {B 10 (Figure 1).…”

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confidence: 99%

closo‐[B₂₁H₁₈]⁻: A Face‐Fused Diicosahedral Borate Ion

et al. 2007

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closo‐[B₂₁H₁₈]⁻: A Face‐Fused Diicosahedral Borate Ion

et al. 2007

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“…For example, B@B 12 H 12 + is a possibility. Hawthorne showed that protonation of dianionic carboranes leads to borane cations, which can be inserted into hydrocarbons 37. This is considered as an example of activation of a boron electrophile, which makes it capable of coordinating with either Bronsted or Lewis acids, and is a fruitful way to allow a wide variety of chemical transformations.…”

Section: Resultsmentioning

confidence: 99%

Cationic Closo Carboranes—Promising Weakly Coordinating Ions

2001

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The unexplored carbon rich cationic closo carboranes, C3Bn−3Hn+1 (n=5, 6, 7, 10, 12) are investigated theoretically. The position isomers were calculated at the B3LYP/6‐31G* level, and the charge distribution in the cluster is estimated by NBO analysis. The criterion of ring‐cap orbital overlap compatibility along with the number of BC, CC, and BB bonds help in explaining the stability order in each category. The most stable isomer is the one with maximum ring‐cap orbital overlap and largest number of BC bonds. The order of relative stability among the trigonal bipyramid is 1c>1b>1a′, where the stability is proportional to the number of CH caps over the small three‐membered ring. The C3B3H6+ isomer with the one allyl C3 group (2b) is more favorable than the one with a cyclopropenyl group (2a). Among the C3B4H7+ isomers the stability order is 3e>3d>3c>3b>3a, which mostly depends on the ring‐cap orbital overlap. In the bicapped square antiprism (4) where there is large number of isomers, the order follows the rule of ring cap compatibility and the number of BC bonds. The order of 5e>5d>5c>5b>5a obtained from the calculations is in perfect agreement with the above sited rules. Equations (1)–(5) devised for estimating the stability of isomers of C3Bn−3Hn+ indicate an increase in stability with cage size. The mono‐positive charge of the isomers is distributed throughout the cage, making them suitable candidates as weakly electrophillic cations. © 2001 John Wiley & Sons, Inc. J Comput Chem 22: 1542–1551, 2001

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“…Hawthorne showed that protonation of dianionic carboranes leads to borane cations, which can be inserted into hydrocarbons. 37 This is considered as an example of activation of a boron electrophile, which makes it capable of coordinating with either Bronsted or Lewis acids, and is a fruitful way to allow a wide variety of chemical transformations. It is expected that the variety of structures studied here with their relative stabilities and charge distribution would encourage fresh attempts at closo carborane cations.…”

Section: Varying Stability Pattern Of Isomers With Number Of Carbon Amentioning

confidence: 99%

Cationic Closo Carboranes—Promising Weakly Coordinating Ions

2001

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ABSTRACT:The unexplored carbon rich cationic closo carboranes, C 3 B n−3 H n +1 (n = 5, 6, 7, 10, 12) are investigated theoretically. The position isomers were calculated at the B3LYP/6-31G * level, and the charge distribution in the cluster is estimated by NBO analysis. The criterion of ring-cap orbital overlap compatibility along with the number of B-C, C-C, and B-B bonds help in explaining the stability order in each category. The most stable isomer is the one with maximum ring-cap orbital overlap and largest number of B-C bonds. The order of relative stability among the trigonal bipyramid is 1c > 1b > 1a , where the stability is proportional to the number of CH caps over the small three-membered ring. The C 3 B 3 H 6 + isomer with the one allyl C3 group (2b) is more favorable than the one with a cyclopropenyl group (2a). Among the C 3 B 4 H 7 + isomers the stability order is 3e > 3d > 3c > 3b > 3a, which mostly depends on the ring-cap orbital overlap. In the bicapped square antiprism (4) where there is large number of isomers, the order follows the rule of ring cap compatibility and the number of B-C bonds. The order of 5e > 5d > 5c > 5b > 5a obtained from the calculations is in perfect agreement with the above sited rules. Equations (1)- (5) devised for estimating the stability of isomers of C 3 B n−3 H n + indicate an increase in stability with cage size. The mono-positive charge of the isomers is distributed throughout the cage, making them suitable candidates as weakly electrophillic cations.

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Electrophilic reactions of protonated closo-B10H102- with arenes, alkane carbon-hydrogen bonds, and triflate ion forming aryl, alkyl, and triflate nido-6-X-B10H13 derivatives

Cited by 47 publications

References 5 publications

closo‐[B₂₁H₁₈]⁻: A Face‐Fused Diicosahedral Borate Ion

closo‐[B₂₁H₁₈]⁻: A Face‐Fused Diicosahedral Borate Ion

Cationic Closo Carboranes—Promising Weakly Coordinating Ions

Cationic Closo Carboranes—Promising Weakly Coordinating Ions

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Electrophilic reactions of protonated closo-B10H102- with arenes, alkane carbon-hydrogen bonds, and triflate ion forming aryl, alkyl, and triflate nido-6-X-B10H13 derivatives

Cited by 47 publications

References 5 publications

closo‐[B21H18]−: A Face‐Fused Diicosahedral Borate Ion

closo‐[B21H18]−: A Face‐Fused Diicosahedral Borate Ion

Cationic Closo Carboranes—Promising Weakly Coordinating Ions

Cationic Closo Carboranes—Promising Weakly Coordinating Ions

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closo‐[B₂₁H₁₈]⁻: A Face‐Fused Diicosahedral Borate Ion

closo‐[B₂₁H₁₈]⁻: A Face‐Fused Diicosahedral Borate Ion