Complexes of functional phosphines

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

doi:10.1016/0022-328x(86)80045-6

Cited by 43 publications

(29 citation statements)

References 13 publications

Supporting

Mentioning

Contrasting

Order By: Relevance

“…In agreement with the proposed structure, the NMR spectra of 20 ± 23 are quite simple and confirm the symmetrical bonding mode of the tridentate [RP(CH 2 CO 2 ) 2 ] 2À unit. The IR spectra of 20 ± 23 display one strong n Ä(CO) band at 1637 or 1647 cm À1 , corresponding to previously published data [22]. In the 1 H-NMR spectra, the diastereoisotopic CH 2 protons of the CH 2 CO 2 fragments give rise to two doublets-of-doublets at d ca.…”

Section: Methodsmentioning

confidence: 57%

Areneruthenium(II) Complexes with Functionalized Phosphines Coordinating as Mono-, Bi- or Tridentate Ligands

Werner¹,

Bank²,

Windmüller³

et al. 2001

HCA

View full text Add to dashboard Cite

Dedicated to the Memory of Luigi M. Venanzi, one of the pioneers of modern coordination chemistry Areneruthenium(II) compounds [Ru(p-cym)Cl 2 {k-P-i PrP(CH 2 CH 2 OMe) 2 }], 3, and [Ru(arene)Cl 2 {k-P-RP(CH 2 CO 2 Me) 2 }] 4 ± 7 (arene p-cym ( 1-methyl-4-isopropylbenzene), mes ( 1,3,5-trimethylbenzene); R i Pr, t Bu) were prepared from the dimers [Ru(arene)Cl 2 ] 2 and the corresponding functionalized phosphine. Treatment of 6 and 7 with 1 equiv. of AgPF 6 affords the monocationic complexes [Ru(mes)Cl{k 2 -P,O-RP(CH 2 C(O)OMe)(CH 2 CO 2 Me)}]PF 6 , 10 and 11, while the related reaction of 5 ± 7 with 2 equiv. of AgPF 6 produces the dicationic compounds [Ru(p-cym){k 3 -P,O,O-t BuP(CH 2 C(O)OMe) 2 }](PF 6 ) 2 (12) and [Ru(mes)-{k 3 -P,O,O-RP(CH 2 C(O)OMe) 2 }](PF 6 ) 2 , 13 and 14. Partial hydrolysis of one hexafluorophosphate anion of 12 ± 14 leads to the formation of [Ru(arene){k 2 -P,O-RP(CH 2 C(O)OMe)(CH 2 CO 2 Me)}(k-O-O 2 PF 2 )]PF 6 , 15 ± 17, of which 17 (arene mes; R t Bu) has been characterized by X-ray crystallography. Compounds 13 and 14 react with 2 equiv. of KO t Bu in t BuOH/toluene to give the unsymmetrical complexes [Ru(mes){k 3 -P,C,O-RP-(CHCO 2 Me)(CHC(O)OMe)}], 18 and 19, containing both a five-membered phosphinoenolate and a threemembered phosphinomethanide ring. The molecular structure of compound 18 has been determined by X-ray structure analysis. The neutral bis(carboxylate)phosphanidoruthenium(II) complexes [Ru(arene){k 3 -P,O,O-RP-(CH 2 C(O)O) 2 }], 20 ± 23 are obtained either by hydrolysis of 18 and 19, or by stepwise treatment of 4 and 5 with KO t Bu and basic Al 2 O 3 . Novel tripodal chelating systems are generated via insertion reactions of 19 with PhNCO and PhNCS.Introduction. ± In the search of finding useful ligands for catalytically active transition-metal complexes, the chemistry of substituted phosphines of general composition R 2 P(CH 2 ) n Y has become an area of great interest in recent years (for reviews, see [1]). By far, the most attention was given to compounds where the functional group Y is MeO, C(O)R' or C(O)OR', since it was anticipated that the Odonors temporarily are able to protect a vacant coordination site and thus allow the addition of more powerful ligands to the metal center under fairly mild conditions. Moreover, with b-phosphino ketones or esters as coordinating groups, a number of Ometallated phosphinoenolate metal complexes have been prepared and found to be appropriate starting materials for C,C coupling reactions with activated alkynes and isocyanates [2], for the generation of metal acetylides from alk-1-ynes [3], and for reversibly binding CO 2 [4].As a continuation of our work on the reactivity of phosphino esters R 2 PCH 2 CO 2 R' toward d 6 and d 8 metal centers [5], we have recently developed a synthetic route to the trifunctional phosphines RP(CH 2 CO 2 R') 2 [6] and started to investigate their coordination capabilities [7]. In this paper, we describe the synthesis of a series of areneruthenium(II) complexes containing the potentially tridentate m...

show abstract

Section: Methodsmentioning

confidence: 57%

Areneruthenium(II) Complexes with Functionalized Phosphines Coordinating as Mono-, Bi- or Tridentate Ligands

Werner¹,

Bank²,

Windmüller³

et al. 2001

HCA

View full text Add to dashboard Cite

show abstract

“…As part of our studies on the coordination chemistry and catalysis with functional phosphine ligands such as b-phosphino-ketones [14], -ester [8], -acids [15], or -amides [16] of type 1, we became interested in incorporating oxazoline moieties in such systems, as shown with 2. For an evaluation of their coordination properties, we first considered four-coordinated palladium(II) complexes and generally observed the formation of strong P,N chelates in complexes such as [PdMe(Cl) (PCH 2 oxazoline)] and [PdMe(SMe 2 )(PCH 2 oxazoline)] (O 3 SCF 3 ) [17].…”

Section: -Allyl Complexesmentioning

confidence: 99%

Functional ligands and complexes for new structures, homogeneous catalysts and nanomaterials

Braunstein

2004

Journal of Organometallic Chemistry

Self Cite

196

View full text Add to dashboard Cite

“…The structure reveals a square-planar rhodium centre co-ordinated by a n-bound cod ligand, a Crystals of complex 17 suitable for a structure determination were grown from CH,Cl,-MeOH (Fig. 44 Crystals of complex 18 were grown by slow diffusion of diethyl ether into a CH,Cl, solution and the molecular structure is shown in Fig. The palladium has a near square-planar geometry with two coordinated anionic bidentate ligands each forming a fivemembered ring (phosphorus trans to nitrogen).…”

Section: Crystal Structures Of Complexes 11718 and 21amentioning

confidence: 99%

“…Pd(L-L)(Ph,PCH=C(OEt)O-P,O}] and [PdCl(L-L)((C,-H, ,),PCMe,CH,COMe-P,O)] (L-L = C9H 12N) 44. Crystals of complex 18 were grown by slow diffusion of diethyl ether into a CH,Cl, solution and the molecular structure is shown in Fig.6(Table…”

mentioning

confidence: 99%

Late transition-metal complexes with the heterofunctional phosphine Ph2PNHP(O)Ph2

Slawin¹,

Smith²,

Woollins³

1996

J. Chem. Soc., Dalton Trans.

View full text Add to dashboard Cite

The complexes [MCl(cod)(HL)] (M = Rh or Ir), [PdCl(q3-C3H,)(HL)], [PdCI(L-L)(HL)], trans-[RhCl(CO)(HL),] and [AuCl(HL)] have been synthesised by reaction of either [{M(p-Cl)(cod)),] (M = Rh or Ir; cod = cycloocta-l,5-diene), [(Pd(p-Cl)(q3-C3H,)) J, [(Pd(p-Cl)(L-L)},] (L-L = C12H12N, C,,H,N or C,H, ,N), [(Rh(p-CI)(CO),),] or [AuCl(tht)] (tht = tetrahydrothiophene) with Ph,PNHP(O)Ph, (HL). In all these complexes the ligand is monodentate P-bound. Chloride abstraction from [PdCI(C, ,H1 ,N)(HL)] or [PdCl(q'-C,H,)(HL)], using Ag[BF,], gave the cationic compounds [Pd(C,,H,,N)(HL)][BF,] or [Pd(q3-C,H,)(HL)][BF,] in which the ligand HL is P,O-chelated. Removal of the amine proton in metal complexes of HL (monodentate P-bound) with KOBu' afforded a new class of neutral metallacycles incorporating either an MP,NO or M,P,N,O, framework based on the [Ph,PNP(O)Ph,]-(L-) ligand. Reaction of [{Pd(p-CI)-(C9H1 ,N)),] with 4 equivalents of HL in methanol at ambient temperature yielded the neutral palladium(I1) complex [PdCl(Ph,PNP(O)Ph,-P,0)(Ph2POMe)] in which one HL ligand has undergone P-N bond scission. The reaction of the iridacycle [Ir(cod){Ph,PNP(O)Ph,-P,O}] with Me1 was shown to proceed with cis addition affording the iridium(m) metallacycle [IrI(Me)(cod)(Ph,PNP(O)Ph,-P,O}]. All compounds described have been characterised by a combination of ' P-[ ' H J NMR spectroscopy, microanalysis and in some cases by 'H NMR and IR spectroscopy. The molecular structures of four complexes have been determined by single-crystal X-ray diffraction. The metallacycles show n-electron delocalisation in the P-N-P-0 fragment. The co-ordination chemistry of Ph,PNHPPh, (dppa)

show abstract

Complexes of functional phosphines

Cited by 43 publications

References 13 publications

Areneruthenium(II) Complexes with Functionalized Phosphines Coordinating as Mono-, Bi- or Tridentate Ligands

Areneruthenium(II) Complexes with Functionalized Phosphines Coordinating as Mono-, Bi- or Tridentate Ligands

Functional ligands and complexes for new structures, homogeneous catalysts and nanomaterials

Late transition-metal complexes with the heterofunctional phosphine Ph2PNHP(O)Ph2

Contact Info

Product

Resources

About