Rhodiumkomplexe mit N-Cyanomethylenimin als Liganden

Steinmetz, M.O.; Werner, Helmut

doi:10.1016/0022-328x(89)85182-4

Cited by 4 publications

(1 citation statement)

References 21 publications

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“…Its mechanism is similar to that of amidocarbonylation. Rhodium complexes with N ‐protected aminomethyl ligands have been prepared from [RhCp(CH 2 I)(I)(PMe 3 )] and amides 12. A general method for the preparation of η 1 ‐aminomethyl and ‐aminoacetyl complexes with a protected amino group is the reaction of anionic organometallic compounds [Co(dimethylglyoximate)] − 13 or of metal carbonyls14,15 with phthaloylmethyl halide, phthaloylglycyl chloride or with mixed anhydrides of N ‐protected α‐amino acids 16,17.…”

Section: Introductionmentioning

confidence: 99%

Aminomethyl and Aminoacetyl Complexes of Palladium(II), Platinum(II), Iron(II) and Rhenium(I) with N‐Phthaloyl as Amino Protecting Group and Mechanistic Studies on the Palladium‐Catalyzed Amidocarbonylation

et al. 2004

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New aminomethyl and aminoacetyl complexes with N‐phthaloyl as the amino protecting group were synthesised by oxidative addition of N‐phthaloylmethyl or ‐acetyl halide to carbonylmetallates or to Pd(PPh3)4 or [Pt(C2H4)(PPh3)2] to give [Re{C(O)CH2N‐phthaloyl}(CO)5] (1), [FeCp(CH2N‐phthaloyl)(CO)2] (2), [FeCp{C(O)CH2N‐phthaloyl}(CO)2] (3), trans‐[PdBr(CH2N‐phthaloyl)(PPh3)2] (4) and trans‐[Pd{C(O)CH2N‐phthaloyl}(X)(PPh3)2] (X = Br, Cl; 5, 6). The bis(phosphane) complexes [Pd(CH2N‐phthaloyl)(X)(R2PCH2CH2PR2)] and [Pd{C(O)CH2N‐phthaloyl}(X)(R2PCH2CH2PR2)] (X = Cl, Br; R = Ph, C6H11) 8−13 were obtained by ligand exchange from 4, 5 or 6 with the corresponding bis(phosphanes). Halide abstraction from 4, 5, 6, 10, 11 or 12 gives the cationic complexes 14 and 15 with formation of a five‐membered chelate ring which includes one carbonyl atom of the phthaloyl group. The reaction of 6 with the tridentate ligand PhP(CH2CH2PPh2)2 affords the five‐coordinate complex 16 and from [Pt(C2H4)(PPh3)2] and organic halides the platinum(II) complexes trans‐[Pt(CH2N‐phthaloyl)(Cl)(PPh3)2] (17) and [PtC(O)CH(CH2Ph)N‐phthaloyl(Cl)(PPh3)2] (18) were isolated. The structures of 2, 11, 14, 15 and 16 were determined by single‐crystal X‐ray analysis. The mechanism of the palladium‐catalysed amidocarbonylation was studied using phthalimide, formaldehyde and CO as a model system which gives N‐phthaloylglycine in good yield. The proposed elementary steps in the palladium‐catalysed amidocarbonylation could be verified by use of the possible intermediates phthaloyl‐NCH2OH and phthaloyl‐NCH2Br as substrates, by oxidative addition of phthaloylmethyl bromide to Pd0, by insertion of CO into the palladium‐carbon‐bond of 4 and 8 with formation of 5 or 9, respectively, and by use of the isolated possible intermediates 4, 5 and 14 as catalysts. Thus, all crucial steps of the palladium‐catalysed amidocarbonylation with the model system phthalimide/formaldehyde/CO have been verified for the first time. (© Wiley‐VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany, 2004)

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Section: Introductionmentioning

confidence: 99%

Aminomethyl and Aminoacetyl Complexes of Palladium(II), Platinum(II), Iron(II) and Rhenium(I) with N‐Phthaloyl as Amino Protecting Group and Mechanistic Studies on the Palladium‐Catalyzed Amidocarbonylation

et al. 2004

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A Novel Route to Formaldehyde and Thioformaldehyde Rhodium Complexes

Werner¹,

Steinmetz

Peters

1998

Eur. J. Inorg. Chem.

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The acetoxymethyl rhodium compounds [(η5‐C5R5)Rh(CH2OAc)(L)I] (4, 13–16) which were prepared from the chloromethyl derivatives [(η5‐C5R5)Rh(CH2Cl)(L)I] and sodium acetate in benzene/acetic acid as solvent, reacted with AgPF6 to give the chelate complexes [(η5‐C5R5)Rh{ĸ2‐C,O‐CH2OC(Me)O}(L)]PF6 (19–23) in excellent yields. Treatment of these complexes with KOH in methanol led to the elimination of the acetyl group and to the formation of the formaldehyde compounds [(η5‐C5R5)Rh(η2‐CH2O)(L)] (24–27). The related thioformaldehyde complexes [(η5‐C5Me5)Rh(η2‐CH2S)(L)] (46, 47) and [(η5‐C5H5)Rh(η2‐CH2S)(PMe3)] (50) were obtained on a similar route. Studies on the reactivity of the formaldehyde derivatives revealed that the Rh–CH2O bond is rather labile and the CH2O ligand easily converted to a CO group.

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