14‐Vertex Heteroboranes with 14 Skeletal Electron Pairs: An Experimental and Computational Study

Robertson, Alasdair P. M.; Beattie, Nicholas A.; Scott, Greig; Man, Wing Y.; Jones, John; Macgregor, Stuart A.; Rosair, Georgina M.; Welch, Alan J.

doi:10.1002/ange.201602440

Cited by 3 publications

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“…DEI was first recognized as a route to bimetallacarboranes by Kudinov and coworkers, 29 and we have previously used it to deliberately prepare 14-vertex bimetallacarboranes from 13-vertex monometallacarborane anions. 16,26,32 In the 1 2. Note that 8 is the complement of 3 in which {CoCp} in 3 has been replaced by {Ru(p-cymene)} and {Ru(p-cymene)} in 3 has been replaced by {CoCp*}.…”

Section: ■ Results and Discussionmentioning

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: ■ Results and Discussionmentioning

confidence: 99%

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

2018

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Synthesis, Structure, Bonding, and Reactivity of Metal Complexes Comprising Diborane(4) and Diborene(2): [{CpMo(CO)₂}₂{μ‐η²:η²‐B₂H₄}] and [{CpM(CO)₂}₂B₂H₂M(CO)₄], M=Mo,W

et al. 2018

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The reaction of [(Cp*Mo)2(μ‐Cl)2B2H6] (1) with CO at room temperature led to the formation of the highly fluxional species [{Cp*Mo(CO)2}2{μ‐η2:η2‐B2H4}] (2). Compound 2, to the best of our knowledge, is the first example of a bimetallic diborane(4) conforming to a singly bridged Cs structure. Theoretical studies show that 2 mimics the Cotton dimolybdenum–alkyne complex [{CpMo(CO)2}2C2H2]. In an attempt to replace two hydrogen atoms of diborane(4) in 2 with a 2e [W(CO)4] fragment, [{Cp*Mo(CO)2}2 B2H2W(CO)4] (3) was isolated upon treatment with [W(CO)5⋅thf]. Compound 3 shows the intriguing presence of [B2H2] with a short B−B length of 1.624(4) Å. We isolated the tungsten analogues of 3, [{Cp*W(CO)2}2B2H2W(CO)4] (4) and [{Cp*W(CO)2}2B2H2Mo(CO)4] (5), which provided direct proof of the existence of the tungsten analogue of 2.

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Synthesis, Structure, Bonding, and Reactivity of Metal Complexes Comprising Diborane(4) and Diborene(2): [{CpMo(CO)₂}₂{μ‐η²:η²‐B₂H₄}] and [{CpM(CO)₂}₂B₂H₂M(CO)₄], M=Mo,W

et al. 2018

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The reaction of [(Cp*Mo) (μ-Cl) B H ] (1) with CO at room temperature led to the formation of the highly fluxional species [{Cp*Mo(CO) } {μ-η :η -B H }] (2). Compound 2, to the best of our knowledge, is the first example of a bimetallic diborane(4) conforming to a singly bridged C structure. Theoretical studies show that 2 mimics the Cotton dimolybdenum-alkyne complex [{CpMo(CO) } C H ]. In an attempt to replace two hydrogen atoms of diborane(4) in 2 with a 2e [W(CO) ] fragment, [{Cp*Mo(CO) } B H W(CO) ] (3) was isolated upon treatment with [W(CO) ⋅thf]. Compound 3 shows the intriguing presence of [B H ] with a short B-B length of 1.624(4) Å. We isolated the tungsten analogues of 3, [{Cp*W(CO) } B H W(CO) ] (4) and [{Cp*W(CO) } B H Mo(CO) ] (5), which provided direct proof of the existence of the tungsten analogue of 2.

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14‐Vertex Heteroboranes with 14 Skeletal Electron Pairs: An Experimental and Computational Study

Cited by 3 publications

References 44 publications

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

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

Synthesis, Structure, Bonding, and Reactivity of Metal Complexes Comprising Diborane(4) and Diborene(2): [{CpMo(CO)₂}₂{μ‐η²:η²‐B₂H₄}] and [{CpM(CO)₂}₂B₂H₂M(CO)₄], M=Mo,W

Synthesis, Structure, Bonding, and Reactivity of Metal Complexes Comprising Diborane(4) and Diborene(2): [{CpMo(CO)₂}₂{μ‐η²:η²‐B₂H₄}] and [{CpM(CO)₂}₂B₂H₂M(CO)₄], M=Mo,W

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14‐Vertex Heteroboranes with 14 Skeletal Electron Pairs: An Experimental and Computational Study

Cited by 3 publications

References 44 publications

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

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

Synthesis, Structure, Bonding, and Reactivity of Metal Complexes Comprising Diborane(4) and Diborene(2): [{Cp*Mo(CO)2}2{μ‐η2:η2‐B2H4}] and [{Cp*M(CO)2}2B2H2M(CO)4], M=Mo,W

Synthesis, Structure, Bonding, and Reactivity of Metal Complexes Comprising Diborane(4) and Diborene(2): [{Cp*Mo(CO)2}2{μ‐η2:η2‐B2H4}] and [{Cp*M(CO)2}2B2H2M(CO)4], M=Mo,W

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Synthesis, Structure, Bonding, and Reactivity of Metal Complexes Comprising Diborane(4) and Diborene(2): [{CpMo(CO)₂}₂{μ‐η²:η²‐B₂H₄}] and [{CpM(CO)₂}₂B₂H₂M(CO)₄], M=Mo,W

Synthesis, Structure, Bonding, and Reactivity of Metal Complexes Comprising Diborane(4) and Diborene(2): [{CpMo(CO)₂}₂{μ‐η²:η²‐B₂H₄}] and [{CpM(CO)₂}₂B₂H₂M(CO)₄], M=Mo,W