Synthesis of (carbyne)metal complexes by oxide abstraction from acyl ligands

Mayr, Andreas; McDermott, Gregory A.; Dorries, Alison M.

doi:10.1021/om00122a035

Cited by 59 publications

(19 citation statements)

References 3 publications

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“…[52] The preparation of benzylidyne complex [PhC MBr 3 (dme)]( 11,M= W, Mo) was first reported by A. Mayr and co-workersint he 1980s. [53] In the first step, M(CO) 6 (M = W,M o) was treated with an ucleophilic aryllithium reagent and NMe 4 Br for cation exchange to form the acyl complexes 10 (Scheme 4). [54] Subsequently,r eaction with oxalyl bromide afforded the Fischerc arbynec omplexes [PhCM(CO) 4 Br] [55] followed by decarbonylation and oxidation with Br 2 at low temperatures to give tribromide complexes 11.…”

Section: Matthiasmentioning

confidence: 99%

Well‐Defined Alkyne Metathesis Catalysts: Developments and Recent Applications

Ehrhorn

Tamm

2018

Chemistry A European J

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Although alkyne metathesis has been known for 50 years, rapid progress in this field has mostly occurred during the last two decades. In this article, the development of several highly efficient andt horoughly studied alkyne metathesis catalysts is reviewed, which includes novel welldefined, in situ formed and heterogeneous systems. Various alkyne metathesis methodologies, including alkyne crossmetathesis (ACM), ring-closing alkyne metathesis (RCAM), cy-clooligomerization,a cyclic diyne metathesis polymerization (ADIMET), and ring-opening alkyne metathesis polymerization (ROAMP), are presented, and their application in natural product synthesis, materials science as well as supramolecular and polymer chemistry is discussed. Recent progress in the metathesis of diynes is also summarized, which gave rise to new methods such as ring-closing diyne metathesis (RCDM)a nd diyne cross-metathesis(DYCM). Scheme1.Mechanism of alkyne metathesis.Scheme2.Synthesis of Schrock's tungsten alkylidyne complex 3.[a] H. Ehrhorn, Prof. Dr.M.T amm Scheme9.Synthesis of molybdenumb enzylidynecomplexes 22 with triphenylsilanolate ligands ;phen = 1,10-phenanthroline.Scheme10. Synthesis of trisilanolate tungsten and molybdenum benzylidyne complexes 25.

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Section: Matthiasmentioning

confidence: 99%

Well‐Defined Alkyne Metathesis Catalysts: Developments and Recent Applications

Ehrhorn

Tamm

2018

Chemistry A European J

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“…[14] The [15,16] The 2-xylyl derivative 1a has been pre-viously employed for the preparation of various ''half-sandwich'' alkylidyne complexes, although its synthesis was not described. [13] The chloro(pyridine)mesitylmethylidyne complex [W(ϵCC 6 H 2 Me 3 -2,4,6)Cl(CO) 2 (NC 5 H 5 ) 2 ] has recently been reported [14] -2,6 2a, C 6 H 2 Me 3 -2,4,6 2b) on the basis of spectroscopic data and a crystallographic study (vide infra) of 2a.…”

Section: Resultsmentioning

confidence: 99%

Dihydrobis(pyrazolyl)borate Alkylidyne Complexes of Tungsten

et al. 2004

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[W(≡CR)Br(CO)2(NC5H4Me‐4)2] (R = C6H3Me2‐2,6 1a, C6H2Me3‐2,4,6 1b) react with K[H2B(pz)2] (pz = pyrazol‐1yl) to provide two interconverting isomers of [W(≡CR)(CO)2(NC5H4Me‐4){H2B(pz)2}] (2), one isomer having been structurally characterised for R = C6H3Me2‐2,6 (2a). The reactions of [W(≡CR)Br(CO)2(CNR′)2] (5: R′ = C6H3Me2‐2,6, CNMe3) with K[H2B(pz)2] or of [W(≡CR)Br(CO)2(NC5H4Me‐4){H2B(pz)2}] (2) with isocyanides are more complex due to the facile formation of unstable ketenyl derivatives. In the absence of light, the reaction of [W(≡CR)Br(CO)2(CNR′)2] (5) with K[H2B(pz)2] provides [W(≡CR)(CO)2(CNR′){H2B(pz)2}] (3) in moderate yield, similar yields were obtained from [W(≡CR)(CO)2(NC5H4Me‐4){H2B(pz)2}] (2) and CNR′. Under mild photolytic conditions both combinations provide primarily the thermally unstable ketenyl complex [W(η2‐OCCR)(CO)(CNR′)2{H2B(pz)2}] (4). The picoline ligand in [W(≡CR)Br(CO)2(NC5H4Me‐4){H2B(pz)2}] (2) is readily replaced by PMe2Ph to provide [W(≡CR)(CO)2(PMe2Ph){H2B(pz)2}] (structurally characterised for R = C6H3Me2‐2,6 6a). The reaction of either [W(≡CR)(CO)2(PMe2Ph){H2B(pz)2}] (6) or [W(≡CR)(CO)2(NC5H4Me‐4){H2B(pz)2}] (R = C6H2Me3‐2,4,6 2b) with excess PMe2Ph provides [W(≡CR)(CO)(PMe2Ph)2{H2B(pz)2}] (7). This complex is also obtained from K[H2B(pz)2] and [W(≡CR)Br(CO)(PMe2Ph)3] (8), the latter arising from the reaction of [W(≡CR)Br(CO)2(NC5H4Me‐4)2] (1b) with PMe2Ph. (© Wiley‐VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany, 2004)

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“…Addition of Li[C Å/C Ã/R] to [M(CO) 6 ] in THF or Et 2 O gave acyl metallates. Subsequent oxide abstraction with trifluoroacetic anhydride at (/80 8C [5] afforded trans-alkynylcarbyne(tetracarbonyl)trifluoroacetato complexes which were transformed into the alkynylcarbyne(dicarbonyl) complexes 1a,b Á/7a,b by addition of bipyridine and 4,4 ?dimethyl-2,2 ?-bipyridine, respectively.…”

Section: Resultsmentioning

confidence: 99%