Carbon−Carbon Bond Activation of R−CN (R = Me, Ar, <sup>i</sup>Pr, <sup>t</sup>Bu) Using a Cationic Rh(III) Complex

Taw, Felicia L.; White, Peter S.; Bergman, Robert G.; Brookhart, Maurice

doi:10.1021/ja0255094

Cited by 145 publications

(94 citation statements)

References 6 publications

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“…Jesson and coworkers (21) have also documented the formation of the cyanomethyl hydride as a result of activation of acetonitrile using (dmpe) 2 M(Np)H (M ϭ Fe, Ru; Np ϭ 2-naphthyl). The scission of the COCN bond of acetonitrile has also been reported by Parkin and coworkers (22), Brookhart and coworkers (23,24), Nakazawa et al (25), and Jones and coworkers (26). Of particular interest is the work by Brookhart using a similar Cp*Rh(PMe 3 ) system (23), which is known to undergo COH bond activation in the presence of alkanes and arenes (3,27).…”

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confidence: 58%

The activation of alkyl cyanides using a rhodiumtrispyrazolylborate complex

Vetter

Rieth

Jones

2007

Proc. Natl. Acad. Sci. U.S.A.

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O rganometallic complexes of the cyclopentadienyl (Cp) and trispyrazolylborate (Tp) type have been shown to activate a variety of COH bonds in alkanes and arenes (1-9). However, studies on the activation of alkanes and arenes containing reactive functional groups have received far less attention in the literature. Hartwig and coworkers (10-12) have been successful in the hydroborylation of mono-and disubstituted arenes using transition metal catalysts. The borylation of the arene ring is believed to occur after oxidative addition of the ring COH bond without interference of reaction with the functional group. Smith (13,14) has even shown that haloarenes can be borylated and functionalized without affecting the carbon-halogen bond. Although numerous examples are presented for the functionalization of substituted arenes (15), the functionalization of alkanes containing reactive functional groups is somewhat restricted, perhaps because some of the functional groups on the alkanes are more reactive toward the catalysts and do not allow for COH activation. In addition, some functional groups (e.g., OH) are known to make the adjacent COH bonds more reactive in alkanes (16).We recently reported the activation of 1-, 2-, and 3-chloropentanes using a trispyrazolylborate rhodium complex (17). It was determined that the [TpЈRh(L)] fragment did not oxidatively cleave the COCl bond of the chloroalkane, as would have been expected given the relative bond strengths of COH (Ϸ100 kcal) vs. COCl (80 kcal) bonds (18) and the literature precedence that exists for the oxidative addition of COCl bonds to Rh(I) and Ir(I) metal systems (15,19). Surprisingly, the [TpЈRh(L)] fragment reacted exclusively with the terminal COH bonds of the alkane to give the substituted haloalkyl hydride complex. Here, we extend the investigation of the activation of hydrocarbon COH bonds to include substrates containing the nitrile functional group (OC'N).The COH bond activation of acetonitrile has been documented in the past. Teuben and coworkers (20) have reported the COH activation of acetonitrile via a -bond metathesis using Cp* 2 LnCH(SiMe 3 ) 2 . Jesson and coworkers (21) have also documented the formation of the cyanomethyl hydride as a result of activation of acetonitrile using (dmpe) 2 M(Np)H (M ϭ Fe, Ru; Np ϭ 2-naphthyl). The scission of the COCN bond of acetonitrile has also been reported by Parkin and coworkers (22), Brookhart and coworkers (23, 24), Nakazawa et al. (25), and Jones and coworkers (26). Of particular interest is the work by Brookhart using a similar Cp*Rh(PMe 3 ) system (23), which is known to undergo COH bond activation in the presence of alkanes and arenes (3,27). However, in the presence of nitriles and triphenylsilane, the complex promotes the cleavage of the COCN bond.To demonstrate the diversity of nitrile reactivity with low valent metals, our group has also investigated the reactions of aromatic, allylic, and alkyl nitriles using [(dippe)NiH] 2 (28-30). In these studies, 2 coordination of the CN bond to the Ni metal cent...

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confidence: 58%

The activation of alkyl cyanides using a rhodiumtrispyrazolylborate complex

Vetter

Rieth

Jones

2007

Proc. Natl. Acad. Sci. U.S.A.

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“…[23] These data, along with its bright orange color,suggest that 7b may be viewed as the first mixed cAAC-isonitrile borylene.…”

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confidence: 92%

From Borane to Borylene without Reduction: Ambiphilic Behavior of a Monovalent Silylisonitrile Boron Species

et al. 2017

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“…Examples of such g 1 -bound aryl complexes are relatively less common in the literature [58][59][60][61][62][63][64][65][66][67][68][69][70][71][72][73]. It may be added in this context that metal mediated C-N bond cleavage, though not very uncommon, is mostly limited to strained amines and amidines [74][75][76][77][78][79], and hence there is significant interest in transition metal mediated C-N bond cleavage [80][81][82][83][84][85][86][87][88][89].…”

Section: Synthesis and Characterizationmentioning

confidence: 99%

Rhodium complexes of 1,3-diaryltriazenes: Usual coordination, N–H bond activation and, N–N and C–N bond cleavage

GuhaRoy¹,

Butcher²,

Bhattacharya³

2008

Journal of Organometallic Chemistry

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Carbon−Carbon Bond Activation of R−CN (R = Me, Ar, ⁱPr, ^tBu) Using a Cationic Rh(III) Complex

Cited by 145 publications

References 6 publications

The activation of alkyl cyanides using a rhodiumtrispyrazolylborate complex

The activation of alkyl cyanides using a rhodiumtrispyrazolylborate complex

From Borane to Borylene without Reduction: Ambiphilic Behavior of a Monovalent Silylisonitrile Boron Species

Rhodium complexes of 1,3-diaryltriazenes: Usual coordination, N–H bond activation and, N–N and C–N bond cleavage

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Carbon−Carbon Bond Activation of R−CN (R = Me, Ar, iPr, tBu) Using a Cationic Rh(III) Complex

Cited by 145 publications

References 6 publications

The activation of alkyl cyanides using a rhodiumtrispyrazolylborate complex

The activation of alkyl cyanides using a rhodiumtrispyrazolylborate complex

From Borane to Borylene without Reduction: Ambiphilic Behavior of a Monovalent Silylisonitrile Boron Species

Rhodium complexes of 1,3-diaryltriazenes: Usual coordination, N–H bond activation and, N–N and C–N bond cleavage

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Carbon−Carbon Bond Activation of R−CN (R = Me, Ar, ⁱPr, ^tBu) Using a Cationic Rh(III) Complex