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*]+

Kudinov, Alexander R.; Rybinskaya, M. I.; Perekalin, Dmitry S.; Meshcheryakov, V. I.; Zhuravlev, Yu. A.; Petrovskii, P. V.; Korlyukov, Alexander A.; Golovanov, Denis G.

doi:10.1007/s11172-005-0056-3

Cited by 10 publications

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“…Compound 6 consists of a 13-vertex docosahedral dicobaltacarborane in which the metal atoms occupy vertices 4 and 5, and the carbon atoms occupy vertices 1 and 12, with a 1′,2′-C 2 B 10 H 11 substituent bound at C12. A handful (<20) of docosahedral MM′C 2 B 9 metallacarboranes are known, and in all structurally established cases ,− the metal atoms occupy the degree-6 vertices 4 and 5, with the carbon atoms either at vertices 1 and 6 or at vertices 2 and 3. Compound 6 is therefore the first proven example of a 13-vertex bimetallacarborane with a 4,5,1,12-M 2 C 2 B 9 architecture, although this motif has previously been suggested for one isomer of (CoCp) 2 C 2 B 9 H 11 .…”

Section: Resultsmentioning

confidence: 99%

Heterometalation of 1,1′-Bis(ortho-carborane)

2018

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Deboronation of [8-(1'- closo-1',2'-CBH)- closo-2,1,8-MCBH] affords diastereoisomeric mixtures of [8-(7'- nido-7',8'-CBH)- closo-2,1,8-MCBH] anions (1, M = Ru( p-cymene); 2, M = CoCp) isolated as [HNMe] salts. Deprotonation of 1 and reaction with CoCl/NaCp followed by oxidation yields [8-(1'-3'-Cp -closo-3',1',2'-CoCBH)-2-( p-cymene)- closo-2,1,8-RuCBH] isolated as two separable diastereoisomers, namely, 3α and 3β, the first examples of heterometalated derivatives of 1,1'-bis( ortho-carborane). Deprotonation of [7-(1'- closo-1',2'-CBH)- nido-7,8-CBH], metalation with CoCl/NaCp* and oxidation affords the isomers [1-(1'- closo-1',2'-CBH)-3-Cp*- closo-3,1,2-CoCBH] (4) and [8-(1'- closo-1',2'-CBH)-2-Cp*- closo-2,1,8-CoCBH] (5) as well as a trace amount of the 13-vertex/12-vertex species [12-(1'- closo-1',2'-CBH)-4,5-Cp*- closo-4,5,1,12-CoCBH] (6). Reduction then reoxidation of 4 converts it to 5. Deboronation of either 4 or 5 yields a diastereoisomeric mixture of [8-(7'- nido-7',8'-CBH)-2-Cp*- closo-2,1,8-CoCBH] (7), again isolated as the [HNMe] salt. Deprotonation of this followed by treatment with [RuCl( p-cymene)] produces [8-(1'-3'-( p-cymene)- closo-3',1',2'-RuCBH)-2-Cp*- closo-2,1,8-CoCBH] (8) as a mixture of two diastereoisomers in a 2:1 ratio, which could not be separated. Diastereoisomers 8 are complementary to 3α and 3β in which {CoCp} and {Ru( p-cymene)} in 3 were replaced by {Ru( p-cymene)} and {CoCp*}, respectively, in 8. Finally, thermolysis of mixture 8 in refluxing dimethoxyethane yields [8-(8'-2'-( p-cymene)- closo-2',1',8'-RuCBH)-2-Cp*- closo-2,1,8-CoCBH] (9), again as a 2:1 diastereoisomeric mixture that could not be separated. All new species were characterized by multinuclear NMR spectroscopy, and 3α, 3β, 4, 5, 6, and 9 were also characterized crystallographically.

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Section: Resultsmentioning

confidence: 99%

Heterometalation of 1,1′-Bis(ortho-carborane)

2018

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“…The structures of 2b, 10 5, and 7b[Co(C 2 B 9 H 11 ) 2 ] 16 were established by X-ray diffraction. Compound 5 possesses the expected 13-vertex closo-dimetallacarborane (Fig.…”

Section: Introductionmentioning

confidence: 99%

Synthesis of 13-vertex dimetallacarboranes by electrophilic insertion into 12-vertex ruthenacarboranes

et al. 2017

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The electrophilic insertion of organometallic species into metallacarboranes was studied in detail for the model compound - the 12-vertex closo-ruthenacarborane anion [Cp*Ru(CBH)] (1). Reactions of the anion 1 with the 12-electron cationic species [M(ring)] (M(ring) = RuCp, RuCp* and Co(CMe)) gave the 13-vertex closo-dimetallacarboranes Cp*Ru(CBH)M(ring). Similar reactions of the neutral ruthenacarborane Cp*Ru(MeS-CBH) produce the cationic dimetallacarboranes [Cp*Ru(MeS-CBH)M(ring)]. The symmetrical 13-vertex diruthenacarboranes (CR)Ru(RCBH)Ru(CR) can be prepared by the direct reactions of Tl[7,8-R-7,8-CBH] (R = H and Me) with two equivalents of [CpRu(MeCN)] or [Cp*RuCl]. The insertions of the 14-electron cationic species [M(ring)] (M(ring) = NiCp, NiCp* and Co(CMe)) into 1 gave the 13-vertex dimetallacarboranes Cp*Ru(CBH)M(ring), which have a distorted framework with one open face. The structures of Cp*Ru(CBH)Co(CMe) and Cp*Ru(CBH)NiCp were established by X-ray diffraction. Some of the 13-vertex dimetallacarboranes have two electrons less than required by Wade's rules. This violation is explained by the absence of the appropriate pathway for the distortion of the framework.

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“…Siebert et al have prepared compounds with a bridging diborole ligand [1][2][3][4][5][6]. We have described previously two l-cyclopentadienyl nikelacarborane complexes [7,8].…”

Section: Introductionmentioning

confidence: 99%