Investigation of the synthesis of {Mo(η5-C5H5)(CO)3}+ fragments partnered with the monoanionic carboranes [closo-CB11H11Br]-, [closo-CB11H6Br6]- and [closo-HCB11Me11]- by silver salt metathesis and hydride abstraction

Nathan J. Patmore, Michael J. Ingleson, Mary F. Mahon, Andrew S. Weller

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18 Citations (Scopus)

Abstract

Abstraction of iodide from [Cp(CO)3MoI] (Cp = η5-C5H5) using the silver salt of the weakly coordinating anion [closo-CB11H11Br]-, initially affords an intermediate dimeric complex, [MoCp(CO)3I·Ag(CB11H11Br)]2, which has a central {AgI}2 core appended by two carborane anions in the solid state. Prolonged reaction does result in elimination of AgI to form [MoCp(CO)3(CB11 H11Br)], but not cleanly. This complex can be isolated in good yield by hydride abstraction from [Cp(CO)3MoH] using the new trityl salt [CPh3][closo-CB11H11Br]. Similarly, reaction of this hydride source with [CPh3][closo-CB11 H6Br6] in CD2Cl2 results in hydride abstraction, but a mixture of products is formed, suggested to consist of the hydride bridged dimer, [{Cp(CO)3Mo}2(μ-H)][closo-CB11 H6Br6], the anion coordinated complex [Cp(CO)3Mo (closo-CB11H6Br6)] and the solvent adduct [Cp(CO)3Mo(ClCD2Cl)] [closo-CB11H6Br6]. Reaction of Ag[closo-HCB11Me11] with [Cp(CO)3MoX] (X = Cl, I) results in a intermediate complex which has a [Cp(CO)3MoX]6Ag2 central core (crystallographically characterised for X = I) with no interactions from the permethylated carborane anions. Prolonged reaction does result in partial AgX elimination to form the halide-bridged dimers [{CpMo(CO)3}2(μ-X)] [closo-HCB11Me11]. Hydride abstraction from [Cp(CO)3MoH] using the new trityl salt [CPh3][closo-HCB11Me11] resulted in the clean formation of the hydride-bridged dimer [{Cp(CO)3Mo}2(μ-H)] [closo-HCB11Me11]. The two anions [closo-CB11H6Br6]- and [closo-HCB11Me11]- have been compared with [B(ArF′)4-] [ArF′ = 3,5-bis(trifluoromethyl)phenyl] in Bullock's ionic hydrogenation of 3-pentanone using [Cp(CO)2(PPh3)Mo]+ catalysts. The permethylated anion slightly outperforms its hexabrominated congener in catalysis, but is still slower than [B(ArF′)4]-.

LanguageEnglish
Pages2894-2904
Number of pages11
JournalDalton Transactions
Issue number14
Early online date18 Jun 2003
DOIs
Publication statusPublished - 21 Jul 2003
Externally publishedYes

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Silver
Hydrides
Anions
Salts
Dimers
Pentanones
Iodides
Catalysis
Hydrogenation
Catalysts

Cite this

@article{9409f0d2dc434b9bb0f0ef95db96fd37,
title = "Investigation of the synthesis of {Mo(η5-C5H5)(CO)3}+ fragments partnered with the monoanionic carboranes [closo-CB11H11Br]-, [closo-CB11H6Br6]- and [closo-HCB11Me11]- by silver salt metathesis and hydride abstraction",
abstract = "Abstraction of iodide from [Cp(CO)3MoI] (Cp = η5-C5H5) using the silver salt of the weakly coordinating anion [closo-CB11H11Br]-, initially affords an intermediate dimeric complex, [MoCp(CO)3I·Ag(CB11H11Br)]2, which has a central {AgI}2 core appended by two carborane anions in the solid state. Prolonged reaction does result in elimination of AgI to form [MoCp(CO)3(CB11 H11Br)], but not cleanly. This complex can be isolated in good yield by hydride abstraction from [Cp(CO)3MoH] using the new trityl salt [CPh3][closo-CB11H11Br]. Similarly, reaction of this hydride source with [CPh3][closo-CB11 H6Br6] in CD2Cl2 results in hydride abstraction, but a mixture of products is formed, suggested to consist of the hydride bridged dimer, [{Cp(CO)3Mo}2(μ-H)][closo-CB11 H6Br6], the anion coordinated complex [Cp(CO)3Mo (closo-CB11H6Br6)] and the solvent adduct [Cp(CO)3Mo(ClCD2Cl)] [closo-CB11H6Br6]. Reaction of Ag[closo-HCB11Me11] with [Cp(CO)3MoX] (X = Cl, I) results in a intermediate complex which has a [Cp(CO)3MoX]6Ag2 central core (crystallographically characterised for X = I) with no interactions from the permethylated carborane anions. Prolonged reaction does result in partial AgX elimination to form the halide-bridged dimers [{CpMo(CO)3}2(μ-X)] [closo-HCB11Me11]. Hydride abstraction from [Cp(CO)3MoH] using the new trityl salt [CPh3][closo-HCB11Me11] resulted in the clean formation of the hydride-bridged dimer [{Cp(CO)3Mo}2(μ-H)] [closo-HCB11Me11]. The two anions [closo-CB11H6Br6]- and [closo-HCB11Me11]- have been compared with [B(ArF′)4-] [ArF′ = 3,5-bis(trifluoromethyl)phenyl] in Bullock's ionic hydrogenation of 3-pentanone using [Cp(CO)2(PPh3)Mo]+ catalysts. The permethylated anion slightly outperforms its hexabrominated congener in catalysis, but is still slower than [B(ArF′)4]-.",
author = "Patmore, {Nathan J.} and Ingleson, {Michael J.} and Mahon, {Mary F.} and Weller, {Andrew S.}",
year = "2003",
month = "7",
day = "21",
doi = "10.1039/B303537A",
language = "English",
pages = "2894--2904",
journal = "Dalton Transactions",
issn = "1477-9226",
publisher = "Royal Society of Chemistry",
number = "14",

}

TY - JOUR

T1 - Investigation of the synthesis of {Mo(η5-C5H5)(CO)3}+ fragments partnered with the monoanionic carboranes [closo-CB11H11Br]-, [closo-CB11H6Br6]- and [closo-HCB11Me11]- by silver salt metathesis and hydride abstraction

AU - Patmore, Nathan J.

AU - Ingleson, Michael J.

AU - Mahon, Mary F.

AU - Weller, Andrew S.

PY - 2003/7/21

Y1 - 2003/7/21

N2 - Abstraction of iodide from [Cp(CO)3MoI] (Cp = η5-C5H5) using the silver salt of the weakly coordinating anion [closo-CB11H11Br]-, initially affords an intermediate dimeric complex, [MoCp(CO)3I·Ag(CB11H11Br)]2, which has a central {AgI}2 core appended by two carborane anions in the solid state. Prolonged reaction does result in elimination of AgI to form [MoCp(CO)3(CB11 H11Br)], but not cleanly. This complex can be isolated in good yield by hydride abstraction from [Cp(CO)3MoH] using the new trityl salt [CPh3][closo-CB11H11Br]. Similarly, reaction of this hydride source with [CPh3][closo-CB11 H6Br6] in CD2Cl2 results in hydride abstraction, but a mixture of products is formed, suggested to consist of the hydride bridged dimer, [{Cp(CO)3Mo}2(μ-H)][closo-CB11 H6Br6], the anion coordinated complex [Cp(CO)3Mo (closo-CB11H6Br6)] and the solvent adduct [Cp(CO)3Mo(ClCD2Cl)] [closo-CB11H6Br6]. Reaction of Ag[closo-HCB11Me11] with [Cp(CO)3MoX] (X = Cl, I) results in a intermediate complex which has a [Cp(CO)3MoX]6Ag2 central core (crystallographically characterised for X = I) with no interactions from the permethylated carborane anions. Prolonged reaction does result in partial AgX elimination to form the halide-bridged dimers [{CpMo(CO)3}2(μ-X)] [closo-HCB11Me11]. Hydride abstraction from [Cp(CO)3MoH] using the new trityl salt [CPh3][closo-HCB11Me11] resulted in the clean formation of the hydride-bridged dimer [{Cp(CO)3Mo}2(μ-H)] [closo-HCB11Me11]. The two anions [closo-CB11H6Br6]- and [closo-HCB11Me11]- have been compared with [B(ArF′)4-] [ArF′ = 3,5-bis(trifluoromethyl)phenyl] in Bullock's ionic hydrogenation of 3-pentanone using [Cp(CO)2(PPh3)Mo]+ catalysts. The permethylated anion slightly outperforms its hexabrominated congener in catalysis, but is still slower than [B(ArF′)4]-.

AB - Abstraction of iodide from [Cp(CO)3MoI] (Cp = η5-C5H5) using the silver salt of the weakly coordinating anion [closo-CB11H11Br]-, initially affords an intermediate dimeric complex, [MoCp(CO)3I·Ag(CB11H11Br)]2, which has a central {AgI}2 core appended by two carborane anions in the solid state. Prolonged reaction does result in elimination of AgI to form [MoCp(CO)3(CB11 H11Br)], but not cleanly. This complex can be isolated in good yield by hydride abstraction from [Cp(CO)3MoH] using the new trityl salt [CPh3][closo-CB11H11Br]. Similarly, reaction of this hydride source with [CPh3][closo-CB11 H6Br6] in CD2Cl2 results in hydride abstraction, but a mixture of products is formed, suggested to consist of the hydride bridged dimer, [{Cp(CO)3Mo}2(μ-H)][closo-CB11 H6Br6], the anion coordinated complex [Cp(CO)3Mo (closo-CB11H6Br6)] and the solvent adduct [Cp(CO)3Mo(ClCD2Cl)] [closo-CB11H6Br6]. Reaction of Ag[closo-HCB11Me11] with [Cp(CO)3MoX] (X = Cl, I) results in a intermediate complex which has a [Cp(CO)3MoX]6Ag2 central core (crystallographically characterised for X = I) with no interactions from the permethylated carborane anions. Prolonged reaction does result in partial AgX elimination to form the halide-bridged dimers [{CpMo(CO)3}2(μ-X)] [closo-HCB11Me11]. Hydride abstraction from [Cp(CO)3MoH] using the new trityl salt [CPh3][closo-HCB11Me11] resulted in the clean formation of the hydride-bridged dimer [{Cp(CO)3Mo}2(μ-H)] [closo-HCB11Me11]. The two anions [closo-CB11H6Br6]- and [closo-HCB11Me11]- have been compared with [B(ArF′)4-] [ArF′ = 3,5-bis(trifluoromethyl)phenyl] in Bullock's ionic hydrogenation of 3-pentanone using [Cp(CO)2(PPh3)Mo]+ catalysts. The permethylated anion slightly outperforms its hexabrominated congener in catalysis, but is still slower than [B(ArF′)4]-.

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U2 - 10.1039/B303537A

DO - 10.1039/B303537A

M3 - Article

SP - 2894

EP - 2904

JO - Dalton Transactions

T2 - Dalton Transactions

JF - Dalton Transactions

SN - 1477-9226

IS - 14

ER -