Metallkomplexe mit biologisch wichtigen Liganden, CXV. Addition von α-Aminosäureestern an [CpFe(CO)3]+: Carbamoylkomplexe Cp(OC)2Fe-C(O)NHCHRCO2R’ und Kristallstruktur von Cp(OC)2Fe-C(O)NHCH2CO2Et / Metal Complexes of Biologically Important Ligands, CXV. Addition of α-Amino Acid Esters to [CpFe(CO)3]+: Carbamoyl Complexes Cp(OC)2Fe-C(O)NHCHRCO2R' and Crystal Structure of Cp(OC)2Fe-C(O)NHCH2CO2Et

1999 ◽  
Vol 54 (3) ◽  
pp. 385-388 ◽  
Author(s):  
Reinhold Urban ◽  
Kurt Polbom ◽  
Wolfgang Beck

α-Amino acid esters can be added to a carbonyl ligand of [CpFe(CO)3]+CF3SO3- to give the carbamoyl complexes Cp(OC)2Fe-C(O)NHCHRCO2R′ (R = H, Me, CHMe2, CH2Ph; R′ = Et, Me). This type of reaction may be useful for the marking of peptides at the amino end. The crystal structure of Cp(OC)2Fe-C(O)NHCH2CO2Et was determined by X-ray diffraction.

1995 ◽  
Vol 73 (7) ◽  
pp. 1164-1174 ◽  
Author(s):  
Doris Freiesleben ◽  
Kurt Polborn ◽  
Christian Robl ◽  
Karlheinz Sünkel ◽  
Wolfgang Beck

Schiff bases from ferrocene aldehyde and α-amino acidates react with PdCl2 or Na2PdCl4 to give N,O-chelate complexes (2a–e, 3). The related N-ferrocenylmethylen-α-amino acid esters give, with Pd(OAc)2, cyclopalladated acetate-bridged complexes (4a,b). N,O-chelate complexes (5–7) are obtained from Na2PdCl4 with N-ferrocenylmethyl prolinate and-alaninate as well as with N,N-dibenzyl glycinate. The ethyl ester of N,N-dibenzylglycine and Pd(OAc)2 form the cyclopalladated acetate-bridged complex 8, while the ester of N-monobenzylglycine and Na2PdCl4 affords trans-PdCl2(L)2 with a monodentate N-coordinated ligand. The structures of 2a, 4a, 5, 7, and 9 were determined by X-ray diffraction. Keywords: ferrocene, amino acids, palladium(II) complexes, crystal structures.


1998 ◽  
Vol 53 (9) ◽  
pp. 965-972 ◽  
Author(s):  
Markus Prem ◽  
Werner Bauer ◽  
Kurt Polbom ◽  
Wolfgang Beck

A series of chelate complexes 1-12 of Cu(II), Ni(II), Pd(II), and Ru(III) with the anion of 2-(2′-hydroxyphenyl)-5(4H)-oxazolone and with 2-(2′-aminophenyl)-5(4H)-oxazolone were prepared from metal salts or from chloro-bridged complexes [(R3P)MCl2]2 (M = Pd, Pt) and [(p-cymene)RuCl2]2. Nucleophilic addition of α-amino acid esters to the bis-chelate complexes M(oxophenyloxazolone)2(M = Ni, Cu) gave the dipeptide derivatives 13-18. Dinuclear Pd(II) and Pt(II) chelate complexes 19-23 were obtained from phenylene- and ethylenebridged bis(oxazolones). The structures of (Et3P)(Cl)Pd(O,N-oxophenyloxazolone) (6) and of Cl2(Et3P)Pt(2,2′-phenylene-bis(4-methyloxazolone)Pt(PEt3)Cl2 (20) were determined by X-ray diffraction. In complex 20 a close proximity of two phenylene H atoms to the metal is observed.


2010 ◽  
Vol 65 (4) ◽  
pp. 503-510 ◽  
Author(s):  
Bernhard Schreiner ◽  
Christian Robl ◽  
Barbara Wagner-Schuh ◽  
Wolfgang Beck

A series of palladium(II) and platinum(II) complexes Cl2M(P-N-O) (M = Pd, Pt) with bidentate Schiff bases (P-N-O) from 2-(diphenylphosphino)benzaldehyde and α-amino acid esters has been synthesized, using PdCl2 or K[PtCl3(C2H4)], respectively. Abstraction of chloride from Cl2M(P-N-O) (using AgBF4) has afforded the cationic complexes [(P-N-O)M(Cl)]+BF4− in which the Schiff bases function as tridentate ligands with coordination of the ester group. The structures of Cl2Pd(Ph2PC6H4C(H)=N-CH2CO2Et) and of [(Cl)Pd(Ph2PC6H4C(H)=NC(H)(CH2CH=CH2)CO2Me)]+BF4− have been determined by X-ray diffraction. Complexes (L)MCl2 and [(L)MCl]+BF4 (M = Pd, Pt) have also been prepared with the reduced Schiff base Ph2PC6H4CH2NHC(H)(CH2Ph)CO2Me.


2010 ◽  
Vol 65 (6) ◽  
pp. 679-686 ◽  
Author(s):  
Bernhard Schreiner ◽  
Barbara Wagner-Schuh ◽  
Wolfgang Beck

The reactions of the chlorido-bridged complexes [Cp*M(Cl)(μ-Cl)]2 (M = Rh, Ir) with Schiff bases (P-N-O) from 2-(diphenylphosphino)benzaldehyde and α-amino acid esters afford the complexes Cp*M(Cl)2(P-N-O) in which the ligands function as monodentate P donors (M = Ir) or as bidentate P-N donors (M = Rh). These complexes can be converted into cationic complexes [Cp*M(Cl)(P-NO)]+ with bidentate P-N ligands by treatment with NH4PF6. The cationic complexes [Cp*M(Cl)(PN- O)]+Cl− have been detected also in solutions of Cp*M(Cl)2(P-N-O). The P-N-coordinated complex [Cp*Rh(Cl)(Ph2P-C6H4-C(H)=N-C(H)(CH2Ph)CO2Me)]+PF6− was characterized by X-ray diffraction. From Cp*M(Cl)2(P-N-O) and AgBF4 or AgPF6 (molar ratio 1 : 2) the dicationic complexes [Cp*M(P-N-O)]2+ are formed in which the ester group is also coordinated to the metal atom. The Schiff base from 2-(diphenylphosphino)benzaldehyde and allylglycine ester acts as a tridentate ligand, however with coordination of the C=C allyl group instead of the ester function.


1996 ◽  
Vol 51 (4) ◽  
pp. 501-505 ◽  
Author(s):  
Wolfgang Weigand ◽  
Michael Weishäupl ◽  
Christian Robl

Abstract The 1-alkyne-1-thiolates R-C ≡C-SLi [1a: R = C(CH3)3, 1b: R = C6H11 ] react with L2PtCl2 (L = PPh3, 1/2 dppe) and CpRu(PPh3)2Cl, respectively to give the complexes trans-(Ph3P)2Pt[S-C ≡C-C(CH3)3]2 (2a), cis-dppePt[S-C≡C-C(CH3)3]2 (2b), and CpRu(PPh3)2-(S-C ≡ C-R) [3a: R = C(CH3)3, 3b: R = C6H11]. 2a has been characterized by 31P CP/MAS NM R spectroscopy and its crystal structure determined by X-ray diffraction.


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