Synthesis of bis[palladium(ii)] and bis[platinum(ii)] complexes containing chiral, linear quadridentate ligands with a P2N2 donor set

Bennett, Justine; Rae, A. David; Salem, Geoffrey; Ward, Natalie C.; Waring, Paul; Wells, Kerri; Willis, Anthony C.

doi:10.1039/b106861j

Cited by 13 publications

(11 citation statements)

References 25 publications

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“…Vinylphosphine 5 was seen as a potential precursor to the elusive quadridentate PN 2 P ligand (R P *,R P *)-and (R P *,S P *)-(CH 2 ) n (PPhC 6 H 4 NH 2 -2) 2 (where n = 2) which cannot be synthesised in the same manner as its analogues (where n = 3-6). 5 The quadridentate ligand (R P *,R P *)-and (R P *,S P *)-…”

Section: Resultsmentioning

confidence: 99%

“…13 (2-Methylaminophenyl)diphenylphosphine, madpp, 12. The salt [Li(tmeda)][2-NHC 6 H 4 PPh 2 (12.5 g, 0.0312 mol) 5 was suspended in thf (400 mL) and the mixture cooled to -78 • C. Methyl iodide (5.12 g, 0.0312 mol) in thf (100 mL) was added dropwise to the stirred suspension. The solution was allowed to warm slowly to ambient temperature and stirred overnight.…”

Section: (±)-(2-aminophenyl)(2-methoxyphenyl)phenylphosphinementioning

confidence: 99%

“…4 Derivatisation of the latter has typically been achieved via reductive cleavage of a phenyl group from adpp using three equivalents of lithium in thf or sodium in liquid ammonia, to give the secondary phosphine (±)-2-H 2 NC 6 H 4 PHPh, (±)-app, 2, upon hydrolysis followed by metallation with sodium in thf and alkylation with, for example, CH 3 I, Br(CH 2 ) n Br (where n = 3-6) or CH 3 C(CH 2 Br) 3 to give (±)-2-H 2 NC 6 H 4 PMePh, (R P *,R P *)and (R P *,S P *)-(CH 2 ) n (PPhC 6 H 4 NH 2 -2) 2 and (R P *,R P *,R P *)-and (R P *,R P *,S P *)-CH 3 C(CH 2 PPhC 6 H 4 NH 2 -2) 3 , respectively. [4][5][6] This approach typically, however, does not allow access to substituted (2-aminophenyl)phosphines of the type (±)-2-H 2 NC 6 H 4 PPhR (where R = aryl or vinyl group). A rare exception is the 2-chlorophenyl substituted PN ligand (±)-(2-aminophenyl)(2chlorophenyl)methylphosphine.…”

Section: Introductionmentioning

confidence: 99%

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Synthesis of 1,3-azaphosphol-2-ones. Crystal and molecular structures of [SP-4-2]-dichlorobis(3-phenyl-1,3-dihydrobenzo[1,3]azaphosphol-2-one-P)palladium(ii) and its chloro(methyl)platinum(ii) analogue

et al. 2010

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Reaction of secondary phosphine (+/-)-(2-aminophenyl)phenylphosphine, (+/-)-app, with PCl(5) in toluene gives the hydrochloride salt of the expected chlorophosphine (+/-)-(2-aminophenyl)chlorophenylphosphine, (+/-)-acpp.HCl, however, this is not the case with triphosgene. Rather the first example of a 1,3-azaphosphol-2-one is isolated, viz. (+/-)-3-phenyl-1,3-dihydrobenzo[1,3]azaphosphol-2-one, (+/-)-pbap. The hydrochloride salt (+/-)-acpp.HCl readily reacts with excess vinyl-, 2-methylphenyl- or 2-methoxyphenyl magnesium bromide to give the corresponding tertiary phosphines (+/-)-(2-H(2)NC(6)H(4))PPhR (where R = CH=CH(2), 2-C(6)H(4)Me or 2-C(6)H(4)OMe). Hydrophosphination of the vinyl substituted tertiary phosphine with (+/-)-app in the presence of KOBu(t) provides a synthetic route to the elusive P(2)N(2) quadridentate ligand (R(P)*,R(P)*)- and (R(P)*,S(P)*)-(CH(2))(2)(PPhC(6)H(4)NH(2)-2)(2), albeit in low yield. The azaphospholone (+/-)-pbap can be readily deprotonated with KOBu(t) in thf and subsequently alkylated with methyl iodide or benzyl bromide to give the analogous N-methyl or N-benzyl derivatives. Alkylation with 1,3-dibromopropane gives the bis(azaphospholone) (R(P)*,R(P)*)- and (R(P)*,S(P)*)-1,3-bis[1-{3-phenyl-1,3-dihydrobenzo[1,3]azaphosphol-2-one}]propane. The latter and the N-methyl substituted azaphospholone can also be synthesised by the reaction of the corresponding secondary phosphine, viz. (R(P)*,R(P)*)- and (R(P)*,S(P)*)-(CH(2))(3)(NHC(6)H(4)PHPh-2)(2) and (+/-)-(2-methylaminophenyl)phenylphosphine, with triphosgene. All three azaphospholones react with [PtClMe(1,5-cyclooctadiene)] in thf to give complexes of the type cis-[PtClMeL(2)] in which ligand L is coordinated via the P atom of the azaphospholones. The ligand (+/-)-pbap has also been complexed to palladium(II) via the reaction with Li(2)[PdCl(4)] in methanol to give cis-[PdCl(2){(+/-)-pbap}(2)]. The structures of cis-[PtClMe{(+/-)-pbap}(2)] and cis-[PdCl(2){(+/-)-pbap}(2)] have been confirmed by X-ray analysis.

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Section: Resultsmentioning

confidence: 99%

Section: (±)-(2-aminophenyl)(2-methoxyphenyl)phenylphosphinementioning

confidence: 99%

Section: Introductionmentioning

confidence: 99%

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Synthesis of 1,3-azaphosphol-2-ones. Crystal and molecular structures of [SP-4-2]-dichlorobis(3-phenyl-1,3-dihydrobenzo[1,3]azaphosphol-2-one-P)palladium(ii) and its chloro(methyl)platinum(ii) analogue

et al. 2010

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“…16 With this in mind, we were looking for a non-silver containing dehalogenating reagent. Therefore, aqueous NH 4 PF 6 , which was earlier used by Bennet et al 17 for the abstraction of chloride anions, was attempted. The driving force for the reaction of 1a and 1b, respectively, with the excess of aqueous NH 4 PF 6 in methanol is the precipitation of the respective ionic complexes 3a and 3b from the reaction mixture.…”

Section: Synthesismentioning

confidence: 99%

Novel enantiopure non-C2-symmetric NCN-pincer palladium complexes with l-proline chiral auxiliaries: mer η3-N,C,N versus square planar η4-N,C,N,O coordination

Gosiewska

Veld

Pater

et al. 2006

Tetrahedron: Asymmetry

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“…In contrast, however, multidentate N , P ligand systems comprising of a diphosphine backbone and two or 35 more peripheral nitrogen donor atom are comparatively rare. Examples of such ligand systems include the N 2 P 2 ligands that contain chiral phosphorus atoms substituted with alkylamine, 20 oxazoline 21 or pyridyl groups. 22 Ligands with up to six mixed N,P donors are rarer still and include the N 2 P 2 N 2 40 tetrapyridyl substituted diphosphphines 23,24 and the potentially hexadentate N,N-dimethylanilinyl substituted diphosphines.…”

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confidence: 99%

Synthesis, characterisation and coordination chemistry of a new multidentate P2N4 ligand system

2009

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A new potentially hexadentate N 2 P 2 N 2 ligand has been prepared and its coordination chemistry to the late transition metal ions Pd(II) and Pt(II) investigated. The ligand bonds in a chelating fashion via the diphosphine backbone to PdCl 2 and PtCl 2 while 10 the appended pyridyl groups remain non-bonding. Abstraction of the chloride ions from the platinum complex results in fluxional exchange of the pyridyl groups in solution at room temperature on the NMR timescale. X-ray crystallographic analysis of this platinum complex revealed a tetracoordinate 15 complex with two bound and two free pyrdyl arms.Ligands that contain a combination of phosphorus and nitrogen donor atoms have been widely studied for their diverse coordination chemistry 1-8 and catalytic applications.

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Synthesis of bis[palladium(ii)] and bis[platinum(ii)] complexes containing chiral, linear quadridentate ligands with a P2N2 donor set

Cited by 13 publications

References 25 publications

Synthesis of 1,3-azaphosphol-2-ones. Crystal and molecular structures of [SP-4-2]-dichlorobis(3-phenyl-1,3-dihydrobenzo[1,3]azaphosphol-2-one-P)palladium(ii) and its chloro(methyl)platinum(ii) analogue

Synthesis of 1,3-azaphosphol-2-ones. Crystal and molecular structures of [SP-4-2]-dichlorobis(3-phenyl-1,3-dihydrobenzo[1,3]azaphosphol-2-one-P)palladium(ii) and its chloro(methyl)platinum(ii) analogue

Novel enantiopure non-C2-symmetric NCN-pincer palladium complexes with l-proline chiral auxiliaries: mer η3-N,C,N versus square planar η4-N,C,N,O coordination

Synthesis, characterisation and coordination chemistry of a new multidentate P2N4 ligand system

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