Investigation in the coupling of zirconocene complexes and trimethylsilyl(diphenylphosphino)acetylene. P–C bond cleavage chemistry from protonolysis reactions

Harouch, Yamna El; Cadierno, Victorio; Igau, Alain; Donnadieu, Bruno; Majoral, Jean‐Pierre

doi:10.1016/j.jorganchem.2003.12.034

Cited by 14 publications

(18 citation statements)

References 47 publications

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“…In 1998, Kazankova and co-workers reported the palladium-catalyzed cross-coupling reaction of silylated vinyl halides with diphenylphosphine for the synthesis of silyl(phosphanyl)alkenes . The addition reactions have been proven to be an alternative route to such alkenes,: for example, additions of a phosphine to silylalkynes (Chart (I)), silylcuprates to alkynylphosphine oxides (Chart (II)), and the in situ generated Cp 2 Zr(η 2 -C 6 H 4 ) to silylphosphanylacetylenes (Chart (III)) . The synthesis of ( Z )-silyl(phosphanyl)alkenes (Chart (IV)) by the addition reaction of silylphosphine to the alkynes has also been reported …”

Section: Introductionmentioning

confidence: 99%

Fine Tuning of the Substituents on the N-Geminal Phosphorus/Silicon-Based Lewis Pairs for the Synthesis of Z-Type Silyliminophosphoranylalkenes

Purushothaman

et al. 2015

Organometallics

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Section: Introductionmentioning

confidence: 99%

Fine Tuning of the Substituents on the N-Geminal Phosphorus/Silicon-Based Lewis Pairs for the Synthesis of Z-Type Silyliminophosphoranylalkenes

Purushothaman

et al. 2015

Organometallics

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“…In related work by Majoral and co-workers, Ph 2 PCtCR alkynes were observed to couple with the transient benzyne complex Cp 2 Zr(η 2 -C 6 H 4 ) to produce the corresponding zirconaindene complexes. 36,37 In the latter compounds, the diphenylphosphino group adopts the R-position of the metallocyclic zirconaindene ring, presumably due to interaction of the lone pair on the phosphorus with the metal center. 36 It has also been proposed that 1-alkynylphosphines and 1-alkynylphosphonates form zirconacyclopropenes as intermediates in zirconocene-mediated cross-couplings with other alkynes.…”

Section: Introductionmentioning

confidence: 99%

Unsymmetrical Zirconacyclopentadienes from Isolated Zirconacyclopropenes with 1-Alkynylphosphine Ligands

et al. 2009

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The reaction of one equiv of 1-alkynylphosphines, R2PCCR′ (R = Et, i Pr, or Ph and R′ = Ph or Mes), with Cp2Zr(pyr)(η2-Me3SiCCSiMe3) resulted in formation of monoalkyne complexes. In the case where R = Et, i Pr, or Ph and R′ = Ph, a “ligand free” zirconacyclopropene complex is produced. These complexes are stabilized by intermolecular donation of the phosphorus lone-pair in the dimeric complexes [Cp2Zr(η2-R2PCCPh)]2 (R = Et, i Pr, or Ph). However, with R = Ph and R′ = Mes, the zirconocyclopropene-pyridine complex Cp2Zr(pyr)(η2-Ph2PCCMes) is formed. Homocoupling of the 1-alkynylphosphines was demonstrated by reaction of a second equiv of Ph2PCCPh with [Cp2Zr(η2-Ph2PCCPh)]2 to give the diphosphinozirconacyclopentadiene Cp2Zr[2,5-(Ph2P)2-3,4-Ph2C4] with high regioselectivity (77%). The zirconacyclopropene complexes also react with one equiv of PhCCPh or EtCCEt to give zirconacyclopentadienes in which the phosphino substituent preferentially adopts the 2-position (α) of the zirconacyclopentadiene ring. These unsymmetrical zirconacyclopentadienes undergo substitution of the R2PCCR′ moiety with the less bulky alkynes PhCCPh or EtCCEt. The substituents on the 1-alkynylphosphines significantly influence the rates of alkyne substitution such that sterically more demanding substituents in either the α- (-P i Pr2) or β- (-Mes) position of the zirconacycle lead to faster exchange. The α-phosphinozirconacyclopentadienes were readily converted to 1-phosphinobutadienes via reaction with benzoic acid. The zirconacyclopentadiene Cp2Zr[2-Ph2P-3,4,5-Ph3C4] was converted to the corresponding thiophene oxide by the oxo-transfer reaction with sulfur dioxide. In the case of ((1Z,3E)-3-ethyl-2-phenylhexa-1,3-dienyl)diphenylphosphine and (3,4,5-triphenylthiophen-2-yl oxide)diphenylphosphine, the molecules were isolated as their phosphine oxides. Reactions of the zirconacyclopropene complexes [Cp2Zr(η2-Ph2PCCPh)]2 and Cp2Zr(pyr)(η2-Ph2PCCMes) with the diyne (F5C6)CC−1,4-C6H4−CC(C6F5) gave bis(zirconacycle)s terminated with phosphino groups. These bis(zirconacycle)s were converted to the corresponding phosphino-terminated oligomers by protonolysis with hydrochloric acid. In addition, the Ph2PCCMes moiety of Cp2Zr[2-Ph2P-3-Mes-4-(C6F5)C4]−1,4-C6H4−Cp2Zr[2-Ph2P-3-Mes-4-(C6F5)C4] was exchanged with PhCCPh to give the phenylene(zirconacyclopentadiene) Cp2Zr[2,3-Ph2-4-(C6F5)C4]−1,4-C6H4−Cp2Zr[2,3-Ph2-4-(C6F5)C4].

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“…[1][2][3][4][5][6][7][8][9][10][11][12][13][14][15][16] Furthermore, these ligands have revealed an interesting reactivity in transition-metal chemistry, such as insertion into reactive M-H or M-C bonds, [17][18][19][20][21][22][23][24][25] intramolecular coupling reactions [10,[26][27][28][29] or P-C bond cleavage to afford alkynide (CϵCR) and phosphide (PPh 2 ) fragments, [6,12,[30][31][32][33][34][35] which are often involved in subsequent coupling or insertion reactions. [36][37][38][39] In addition, simple P-coordination of alkynylphosphanes polarizes the electron density of the alkyne function by concentrating it on the C α atom, which favours its interaction with electrophilic and nucleophilic substrates such as water, [40,41] ethanol, [42,43] HX, …”

Section: Introductionmentioning

confidence: 99%

Ethynyltolan Platinum Complexes with (Arylalkynyl)phosphane Ligands

García

Lalinde

2007

Eur J Inorg Chem

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The ethynyltolan mononuclear complexes cis‐[Pt(C≡CC6H4C≡CPh)2(PPh2C≡CR)2] [R = tol (2), C6H4C≡CPh (3)], which contain (arylalkynyl)phosphane ligands, were prepared, and the X‐ray molecular structure of 2 was determined. The reaction of 2 and 3 with cis‐[Pt(C6F5)2(thf)2] (thf = tetrahydrofuran) in the appropriate molar ratio gave the dinuclear platinum derivatives cis‐[{Pt(PPh2C≡CR)2(μ‐η1:η2‐Cα,Cβ‐C≡CC6H4C≡CPh)2}Pt(C6F5)2] [R = tol (4), C6H4C≡CPh (5)] and the trinuclear derivatives [{Pt(μ‐η1:η2‐Cα,Cβ‐C≡CC6H4C≡CPh)2(μ‐1κP:2η2‐Cα,Cβ‐PPh2C≡CR)2}{Pt(C6F5)2}2][R = tol (6), C6H4C≡CPh (7)], which are stabilized by a double ethynyltolan bridging system or a mixed ethynyltolan/alkynylphosphane bridging system, respectively.(© Wiley‐VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany, 2007)

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Investigation in the coupling of zirconocene complexes and trimethylsilyl(diphenylphosphino)acetylene. P–C bond cleavage chemistry from protonolysis reactions

Cited by 14 publications

References 47 publications

Fine Tuning of the Substituents on the N-Geminal Phosphorus/Silicon-Based Lewis Pairs for the Synthesis of Z-Type Silyliminophosphoranylalkenes

Fine Tuning of the Substituents on the N-Geminal Phosphorus/Silicon-Based Lewis Pairs for the Synthesis of Z-Type Silyliminophosphoranylalkenes

Unsymmetrical Zirconacyclopentadienes from Isolated Zirconacyclopropenes with 1-Alkynylphosphine Ligands

Ethynyltolan Platinum Complexes with (Arylalkynyl)phosphane Ligands

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