Complexes of functional phosphines. 10. Palladium complexes with the ligands (diphenylphosphino)acetophenone, (Ph2PCHCOPh)- and Ph2PCHC(Ph)OPPh2. Crystal and molecular structure of cis-[PdCl2{Ph2PCH:C(Ph)OPPh2}]

Bouaoud, Salah-Eddine; Braunstein, Pierre; Grandjean, Daniel; Matt, Dominique; Nobel, Dominique

doi:10.1021/ic00241a012

Cited by 93 publications

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“…Interestingly the NsH protons in the ligand (which were located by ∆F maps) are no longer syn with respect to the PdO Previous work has demonstrated that -ketophosphine metal complexes can be deprotonated to afford coordinated phosphino enolate ligands. [51][52][53][54][55][56] Using a suitable base (e.g. the metal alkoxide t BuOK) we find that the acidic proton of the bound HL ligand in the complexes 4 and 5 are readily removed, affording the bischelate complexes [M{Ph 2 PNP(O)Ph 2 -P,O} 2 ] [M ) Pt (10); M ) Pd (11)] (Scheme 2).…”

Section: Resultsmentioning

confidence: 99%

Palladium(II) and Platinum(II) Complexes of the Heterodifunctional Ligand Ph₂PNHP(O)Ph₂

et al. 1996

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The noncomplexed ligand Ph 2 PNHP(O)Ph 2 (HL) has been prepared, for the first time, from Ph 2 PNHPPh 2 (dppa) and H 2 O 2 in moderate yield. On further treatment with H 2 O 2 the phosphine oxide Ph 2 P(O)NHP(O)Ph 2 (1) can be formed. Reaction of [MCl 2 (COD)] (M ) Pt or Pd; COD ) cycloocta-1,5-diene) with 2 molar equiv of HL affords [MCl 2 (HL) 2 ] (4, 5) in which both ligands are monodentate P-bound. The analogous dibromo and diiodo derivatives [MX 2 (HL) 2 ] (6-9) were prepared from either [MX 2 (COD)] (M ) Pt or Pd; X ) Br or I) and HL or treatment of [MCl 2 (HL) 2 ] with an excess of NaI. Facile base deprotonation of the amine proton in 4 or 5 affords a new class of metallacycles [M(L) 2 ] [L -) Ph 2 PNP(O)Ph 2 -] (10, 11) incorporating two five-membered M-P-N-P-O rings. Compound 10 was independently made from [Pt(CH 3 ) 2 (COD)] and 2 equiv of HL in toluene at ambient temperature whereas the reaction of [Pt(CH 3 )Cl(COD)] with 2 equiv of HL affords solely trans-[Pt-(CH 3 )Cl(HL) 2 ] (13). Protonation of the neutral compound 10 with HCl in ethanol regenerates the ring-opened cis complex 4. In contrast, addition of HBF 4 ‚OEt 2 to 10 (or 11) results in exclusive protonation at the nitrogen atom of the chelating ligands to give cis-[M{Ph 2 PNHP(O)Ph 2 -P,O} 2 ][BF 4 ] 2 (15, 16); both chelate rings remain intact. The dicationic compounds 15, 16 can also be synthesized from 4, 5 in dichloromethane using Ag[BF 4 ] as a chloride abstractor. All new compounds described have been characterized by a combination of multinuclear NMR spectroscopy, IR spectroscopy, and elemental analyses. The molecular structures of Ph 2 PNHP(O)Ph 2 , cis-[PtBr 2 {Ph 2 PNHP(O)Ph 2 -P} 2 ], cis-[Pt{Ph 2 PNP(O)Ph 2 -P,O} 2 ], trans-[Pt(CH 3 )Cl{Ph 2 PNHP(O)Ph 2 -P} 2 ] and cis-[Pt{Ph 2 PNHP(O)Ph 2 -P,O} 2 ][BF 4 ] 2 have been determined by single-crystal X-ray diffraction. Crystals of HL are triclinic, space group P1 h, with a ) 10.410(2) Å, b ) 12.083(2) Å, c ) 9.036(4) Å, R ) 103.05(2)°, ) 99.09-(2)°, γ ) 72.98(1)°, V ) 1054 Å 3 , and Z ) 2. The final R and R w values were 0.061 and 0.047, respectively. Crystals of 6 are triclinic, space group P1 h, with a ) 13.113(4) Å, b ) 15.996(4) Å, c ) 13.011(4) Å, R ) 102.65(3)°, ) 117.39(2)°, γ ) 101.03(2)°, V ) 2225 Å 3 , and Z ) 2. The final R and R w values were 0.039 and 0.031, respectively. Crystals of 10 are monoclinic, space group P2 1 /a, with a ) 17.600(13) Å, b ) 13.498-(10) Å, c ) 18.641(9) Å, ) 105.13(1)°, V ) 4274 Å 3 , and Z ) 4. The final R and R w values were 0.041 and 0.036, respectively. Crystals of 13 are triclinic, space group P1 h, with a ) 14.686(2) Å, b ) 18.735(2) Å, c ) 9.018(3) Å, R ) 91.71(2)°, ) 102.27(2)°, γ ) 68.54(1)°, V ) 2253 Å 3 , and Z ) 2. The final R and R w values were 0.041 and 0.044, respectively. Crystals of 15 are orthorhombic, space group P2 1 2 1 2, with a ) 14.100(2) Å, b ) 19.002(1) Å, c ) 9.145(2) Å, V ) 2450 Å 3 , and Z ) 2. The final R and R w values were 0.052 and 0.057, respectively. The P-bound monodentate complexes contain ligands with similar...

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Section: Resultsmentioning

confidence: 99%

Palladium(II) and Platinum(II) Complexes of the Heterodifunctional Ligand Ph₂PNHP(O)Ph₂

et al. 1996

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“…. O)Ph system, respectively [12]. Furthermore, the 13 C{ 1 H} NMR data also confirmed the presence of two types of C-O carbons with resonances at 192.6 and 186.5 ppm for the uncoordinated ketone group and the O-coordinated enolate function, respectively.…”

Section: Resultsmentioning

confidence: 59%

“…The reaction of [Ir(cod)(m-Cl)] 2 with 2 equivalents of the ketophosphine Ph 2 PCH 2 C(O)Ph in the presence of TlPF 6 afforded the octahedral phosphino-enolate Ir(III) hydrido complex 4 as (8), C21-C22 1.513(9), O1-C2 1.347 (7), O2-C22 1.220 (7); P1-Ir1-P2 100.21(6), P1-Ir1-O1 81.74(11), P2-Ir1-O1 84.85 (12).…”

Section: Resultsmentioning

confidence: 99%

Room-temperature C–H activation of the phosphino-ketone Ph2PCH2C(O)Ph leading to an iridium(III) complex with a hybrid phosphino-enolate ligand

Liu

Boucher

Frémont

et al. 2015

Comptes Rendus. Chimie

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“…Similarly to the phosphino-ester ligand Ph 2 PCH 2 C(O)OEt, the phosphino-ketone Ph 2 PCH 2 C(O)Ph was found to chelate transition metals and its easy and modular synthesis prompted numerous studies in coordination chemistry [25]. It was rapidly found that when this ligand is coordinated to a transition metal, either j , weak bases being sufficient as a result of the enhanced acidity of the PCH 2 protons upon coordination [26].…”

Section: Metal Complexes With Po-type Ligandsmentioning

confidence: 99%

“…It is plausible that 31 could be accessible from the reaction of the corresponding Grignard reagent with IPr in the presence of dioxane. The structures of the underligated complexes 21,22,24,25,[27][28][29][30] are shown in Figures 9-16 Synthetic transformations leading to 3-coordinate, underligated chlorido-alkyl and di-alkyl iron, chlorido-alkyl magnesium, alkyl cobalt and dibenzyl chromium complexes.…”

Section: N1 Fe1 Cl1mentioning

confidence: 99%

Ligand Control of the Metal Coordination Sphere: Structures, Reactivity and Catalysis

Danopoulos

Braunstein

2016

Oil Gas Sci. Technol. – Rev. IFP Energies nouvelles

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Dedicated to the memory of Yves Chauvin, a most remarkable and visionary man and scientist, with gratitude for our scientific and non-scientific conversations and a very fruitful and enjoyable collaboration.Abstract -Two major aspects of coordination/organometallic chemistry are discussed in this article: (i) the use of functional chelating ligands to stabilize metal complexes while allowing easy stereodifferentiation within the coordination sphere and (ii) the choice of suitable ligands to stabilize challenging 'underligated' metal complexes with electronically highly unsaturated metal centres, thus potentially displaying unusual reactivity. In both cases, the relevance to homogeneous catalysis will be discussed.Résumé -Contrôle de la sphère de coordination des métaux par les ligands : structures, réacti-vité et catalyse -Deux aspects majeurs de la chimie de coordination/organométallique sont discutés dans cet article : d'une part, l'utilisation de ligands chélatants fonctionnels pour stabiliser des complexes métalliques en permettant une différenciation stéréoélectronique aisée au sein de la sphère de coordination et, d'autre part, la sélection de ligands adaptés à la stabilisation de complexes métalliques sous-coordinés dont les centres métalliques sont hautement insaturés électroniquement et donc potentiellement le siège d'une réactivité inhabituelle. Dans les deux cas, nous évoquerons la pertinence de ces approches en catalyse homogène.

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Complexes of functional phosphines. 10. Palladium complexes with the ligands (diphenylphosphino)acetophenone, (Ph2PCHCOPh)- and Ph2PCHC(Ph)OPPh2. Crystal and molecular structure of cis-[PdCl2{Ph2PCH:C(Ph)OPPh2}]

Cited by 93 publications

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Palladium(II) and Platinum(II) Complexes of the Heterodifunctional Ligand Ph₂PNHP(O)Ph₂

Palladium(II) and Platinum(II) Complexes of the Heterodifunctional Ligand Ph₂PNHP(O)Ph₂

Room-temperature C–H activation of the phosphino-ketone Ph2PCH2C(O)Ph leading to an iridium(III) complex with a hybrid phosphino-enolate ligand

Ligand Control of the Metal Coordination Sphere: Structures, Reactivity and Catalysis

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Complexes of functional phosphines. 10. Palladium complexes with the ligands (diphenylphosphino)acetophenone, (Ph2PCHCOPh)- and Ph2PCHC(Ph)OPPh2. Crystal and molecular structure of cis-[PdCl2{Ph2PCH:C(Ph)OPPh2}]

Cited by 93 publications

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Palladium(II) and Platinum(II) Complexes of the Heterodifunctional Ligand Ph2PNHP(O)Ph2

Palladium(II) and Platinum(II) Complexes of the Heterodifunctional Ligand Ph2PNHP(O)Ph2

Room-temperature C–H activation of the phosphino-ketone Ph2PCH2C(O)Ph leading to an iridium(III) complex with a hybrid phosphino-enolate ligand

Ligand Control of the Metal Coordination Sphere: Structures, Reactivity and Catalysis

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Palladium(II) and Platinum(II) Complexes of the Heterodifunctional Ligand Ph₂PNHP(O)Ph₂

Palladium(II) and Platinum(II) Complexes of the Heterodifunctional Ligand Ph₂PNHP(O)Ph₂