Direct Electrophilic Insertion into a Twelve-Vertex Metallacarborane

Kudinov, Alexander R.; Perekalin, Dmitry S.; Rynin, Stanislav S.; Grintselev-Knyazev, Gennadii V.; Petrovskii, P. V.

doi:10.1002/1521-3773(20021104)41:21<4112::aid-anie4112>3.0.co;2-y

Cited by 33 publications

(18 citation statements)

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“…Direct electrophilic insertion, a term coined by Kudinov and co-workers, 23 involves the polyhedral expansion of an anionic closo metallacarborane by its reaction with a cationic metal fragment. It is a complement to direct nucleophilic insertion of zerovalent metal fragments into neutral closo carboranes and metallacarboranes developed by Stone, Green and co-workers several decades ago, 24 with both approaches offering interesting alternatives to the traditional method of polyhedral expansion via the two-stage approach of 2-e reduction followed by metallation.…”

Section: Mechanistic Implicationsmentioning

confidence: 99%

Asymmetric 1,8/13,2,x-M₂C₂B₁₀14-vertex metallacarboranes by direct electrophilic insertion reactions; the VCD and BHD methods in critical analysis of cage C atom positions

et al. 2014

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The isolation of six isomeric, low-symmetry, dicobaltacarboranes with bicapped hexagonal antiprismatic cage structures, always in low yield, is described from reactions in which 13-vertex cobaltacarborane anions and sources of cobalt-containing cations were present. The vertex-to-centroid distance (VCD) and boron-H distance (BHD) methods are used to locate the correct C atom positions in the cages, thus allowing the compounds to be identified as 1,13-Cp2-1,13,2,10-closo-Co2C2B10H12 (1), 1,8-Cp2-3-OEt-1,8,2,10-closo-Co2C2B10H11 (2), 1,13-Cp2-1,13,2,9-closo-Co2C2B10H12 (3), 1,8-Cp2-1,8,2,4-closo-Co2C2B10H12 (4), 1,13-Cp2-1,13,2,4-closo-Co2C2B10H12 (5) and 1,8-Cp2-1,8,2,5-closo-Co2C2B10H12 (6). It is shown that a common alternative method of cage C atom identification, using refined (as B) U(eq) values, does not work well, at least in these cases. Having identified the correct isomeric forms of the six dicobaltacarboranes, their syntheses are tentatively rationalised in terms of the direct electrophilic insertion of a {CpCo(+)} fragment into [CpCoC2B10](-) anions and it is demonstrated that compounds 1, 4, 5 and 6 can be successfully prepared by deliberately performing such reactions.

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Section: Mechanistic Implicationsmentioning

confidence: 99%

Asymmetric 1,8/13,2,x-M₂C₂B₁₀14-vertex metallacarboranes by direct electrophilic insertion reactions; the VCD and BHD methods in critical analysis of cage C atom positions

et al. 2014

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“…We have previously rationalized the formation of 1,13,2,9‐M 2 C 2 B 10 and related asymmetric 14‐vertex dimetallacarboranes by direct electrophilic insertion (DEI) of a cationic metal fragment into an effectively closo monoanionic metallacarborane cage, in contrast to formal two‐electron reduction followed by metalation. Whilst reduction–metalation of 4,1,8‐MC 2 B 10 leads to 1,14,2,9‐MM′C 2 B 10 species, DEI of 4,1,8‐MC 2 B 10 affords a 1,13,2,9‐MM′C 2 B 10 product.…”

Section: Figurementioning

confidence: 79%

Carborane Substituents Promote Direct Electrophilic Insertion over Reduction–Metalation Reactions

et al. 2016

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Two-electron reduction of 1,1'-bis(o-carborane) followed by reaction with [Ru(η-mes)Cl2 ]2 affords [8-(1'-1',2'-closo-C2 B10 H11 )-4-(η-mes)-4,1,8-closo-RuC2 B10 H11 ]. Subsequent two-electron reduction of this species and treatment with [Ru(η-arene)Cl2 ]2 results in the 14-vertex/12-vertex species [1-(η-mes)-9-(1'-1',2'-closo-C2 B10 H11 )-13-(η-arene)-1,13,2,9-closo-Ru2 C2 B10 H11 ] by direct electrophilic insertion, promoted by the carborane substituent in the 13-vertex/12-vertex precursor. When arene=mesitylene (mes), the diruthenium species is fluxional in solution at room temperature in a process that makes the metal-ligand fragments equivalent. A unique mechanism for this fluxionality is proposed and is shown to be fully consistent with the observed fluxionality or nonfluxionality of a series of previously reported 14-vertex dicobaltacarboranes.

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“…Earlier, 6 we have found that the reactions of the ac etonitrile complexes [(C 5 R 5 )Ru(MeCN) 3 ] + with the ruthenacarborane anion [Cp*Ru(η 7,8 C 2 B 9 H 11 )]are accompanied by the electrophilic insertion of the [(C 5 R 5 )Ru] + fragments into the cage to form 13 vertex diruthenacarboranes (C 5 R 5 )Ru(C 2 B 9 H 11 )RuCp* (5a,b). The structure of complex 5b was confirmed by X ray dif fraction analysis.…”

Section: Resultsmentioning

confidence: 99%

Structures of cationic metallacarborane complexes [(η-9-Me2S-7,8-C2B9H10)Ni(μ-Cp)Ni(η-9-Me2S-7,8-C2B9H10)]+ and [CpRu(Me2S-C2B9H10)RuCp]+

et al. 2004

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Direct Electrophilic Insertion into a Twelve-Vertex Metallacarborane

Cited by 33 publications

References 1 publication

Asymmetric 1,8/13,2,x-M₂C₂B₁₀14-vertex metallacarboranes by direct electrophilic insertion reactions; the VCD and BHD methods in critical analysis of cage C atom positions

Asymmetric 1,8/13,2,x-M₂C₂B₁₀14-vertex metallacarboranes by direct electrophilic insertion reactions; the VCD and BHD methods in critical analysis of cage C atom positions

Carborane Substituents Promote Direct Electrophilic Insertion over Reduction–Metalation Reactions

Structures of cationic metallacarborane complexes [(η-9-Me2S-7,8-C2B9H10)Ni(μ-Cp)Ni(η-9-Me2S-7,8-C2B9H10)]+ and [CpRu(Me2S-C2B9H10)RuCp]+

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Direct Electrophilic Insertion into a Twelve-Vertex Metallacarborane

Cited by 33 publications

References 1 publication

Asymmetric 1,8/13,2,x-M2C2B1014-vertex metallacarboranes by direct electrophilic insertion reactions; the VCD and BHD methods in critical analysis of cage C atom positions

Asymmetric 1,8/13,2,x-M2C2B1014-vertex metallacarboranes by direct electrophilic insertion reactions; the VCD and BHD methods in critical analysis of cage C atom positions

Carborane Substituents Promote Direct Electrophilic Insertion over Reduction–Metalation Reactions

Structures of cationic metallacarborane complexes [(η-9-Me2S-7,8-C2B9H10)Ni(μ-Cp)Ni(η-9-Me2S-7,8-C2B9H10)]+ and [Cp*Ru(Me2S-C2B9H10)RuCp*]+

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Asymmetric 1,8/13,2,x-M₂C₂B₁₀14-vertex metallacarboranes by direct electrophilic insertion reactions; the VCD and BHD methods in critical analysis of cage C atom positions

Asymmetric 1,8/13,2,x-M₂C₂B₁₀14-vertex metallacarboranes by direct electrophilic insertion reactions; the VCD and BHD methods in critical analysis of cage C atom positions

Structures of cationic metallacarborane complexes [(η-9-Me2S-7,8-C2B9H10)Ni(μ-Cp)Ni(η-9-Me2S-7,8-C2B9H10)]+ and [CpRu(Me2S-C2B9H10)RuCp]+