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  • Author: Karlheinz Sünkel x
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Treatment of the cymantrene thioether [C5(SMe)5]Mn(CO)3 (IIb) with Na2PdCl4 or K2PtCl4 yields the bimetallic chelate complexes [C5(SMe)5]Mn(CO)3*MCl2 (M = Pd (2) or Pt (3)). Similarly, the S,P-chelate complexes [C5Cl2(SR)2(PPh2)]Mn(CO)3*PdCl2 (R = Me (4a), Ph (4b)) can be obtained from the corresponding mononuclear cymantrene derivatives and Na2PdCl4 or (PhCN)2PdCl2. Analysis of the 1H NMR spectra only allows for the Pt complex the identification of one meso form, which seems to be favoured by 2:1, together with the D,L forms. The crystal structures of [C5Cl2(SMe)3]Mn(CO)3*PdCl2(1, C11H9Cl4MnO3PdS3, triclinic, P1̄, a = 7.617(3) Å , b = 10.528(4) Å ,c = 12.473(5) Å , α = 72.95(3)°, β = 84.94(3)°, γ = 88.75(3)°, V = 952.6(6) Å3, Z = 2), 2 (C13H15Cl2MnO3PdS5, orthorhombic, Pn21/c, a = 12.739(5) Å , b = 9.992(3) Å , c = 16.884(5) Å , V = 2149(1) Å, Z = 4), and 4 (C23H18Cl6MnO3PPdS2, monoclinic, P21/c, a = 13.199(4) Å , b = 29.198(11) Å , c = 15.921(7) , β - 101.41(3)°, V = 6015(4) Å3, Z = 8) are reported and compared with each other and other bimetallic metallocene phosphine and thioether derivatives.

The anions of hydantoin (L1) and of the imide of 3,4-pyridine dicarboxylic acid (L2) form the complexes Ph3PAu(L1-H+) (1), Ph3PAu(L2-H+) (2), (nBu3P)2Ni(L1-H+)2 (3) and the ligand bridged compounds Ph3PAu(L2-H+)M(PEt3)Cl2 (M = Pd, Pt, 4, 5). With the neutral ligand L2 the complexes Cp*Ir(Cl)2(L2) (6), (ρ-cymene)Ru(Cl)2 (L2) (7) and (Et3P)(Cl)2Pd(L2) (8) were obtained. Complexes 1, 2 and 6 were characterized by X-ray diffraction.

Chiral Cyclopentadienyl Complexes, Crystal Structure

The reaction of [C5Cl4(SMe)]Mn(CO)3 (la) with n-butyllithium and the electrophiles SiMe3Cl, CO2, or PPh2Cl regiospecifically yields the chiral 1,3-disubstituted functional cymantrene thioethers [C5Cl3(SMe)R]Mn(CO)3 (R = SiMe3 (2), COOLi (3a), PPh2 (4)). 3 a can be protonated to give the corresponding carboxylic acid (3b), which in turn can be transformed to the acid chloride [C5Cl3(SMe)(COCl)]Mn(CO)3 (3c). 3c reacts with NaN3 to yield after work-up the urea derivative OC[[NH—C5Cl3(SMe)]Mn(CO)3]2 (3d). Using the cymantrene bisthioethers [C5Cl3(SR)2]Mn(CO)3 (R = Me, 5a, Ph, 5b) as starting materials, the carboxyl derivatives [C5Cl2(SMe)2(COR)]Mn(CO)3 (R = OLi, 6a, OH, 6b, Cl, 6c) and the potential organometallic S,P-chelate ligands [C5Cl2(SR)2(PPh2)]Mn(CO)3 (R = Me, 7a, Ph, 7b) can be obtained. The crystal structure determination of 7a (C22H16O3PS2Cl2Mn, monoclinic, P 21/c, a = 18.714(6) A, b = 9.506(3) A, c = 14.475(3) Α, β = 109.18(2)°, V = 2432.1(12) Α3, Z = 4) shows an orientation of the neighbouring PPh2- and SMe groups, that allows chelation of an additional metal fragment.

The structure of the title complex consists of [Ir3(C5Me5)3(L-prolinate)3]3+ complex cations and CF3SO3 - anions. Each iridium atom is coordinated in a distorted tetrahedral manner by one cyclopentadienyl group, two carboxylate O atoms and the prolinate N atom. The iridium atoms are bridged by the carboxylate groups. Each of the three stereogenic iridium atoms has the same (S) configuration, i. e. the trimerization of the [Ir(C5Me5)(L-prolinate)]+ fragment occurs with chiral self recognition.


Tetrafluoroborate complexes (η5 -C5H5)Mo(CO)2(PR3)FBF3 have been prepared by hydride abstraction from the corresponding hydrido compounds using Ph3CBF4. The tetrafluoroborate ligand in (η5 -C5H5)Mo(CO)2(L)FBF3 (L = CO, PR3) is easily sub-stituted by phosphanes, cis-and trans-butene(2), a-acetamidocinnamic acid and buta-diene. Nucleophilic addition of HNMe2 to the butadiene complex [(η5 -C5H5)Mo(CO)3 butadiene)]+BF4 - gives the β-aminoacyl chelate compound 7.

A series of complexes with anions of N-[1,2:3,4-di-O-isopropylidene-6-deoxy-α-D-galactopvranos-6-yl]-α-aminoacids has been obtained and characterized by spectroscopic data: 1-4 (R' = 6-deoxy-galactopyranosyl), (η5-C5Me5)(Cl) 5, 6 (M = Rh, Ir), (η5-C5Me5)M(CH3SCH2CH2CH(CO2)NHR') 7,8 (M = Rh, Ir), M(NHR 'CHRCO2)2 9-16 (M = Cu, Pd), (η2-C2H4)(Cl)Pt(NHR'CHRCO2) 17-20, Cl2M(CH3SCH2CH2CH(CO2R)NHR) 21-24 (M = Pd, Pt), Cl2M(NHR'CHRCO2Me)2 25-31 (M = Pd, Pt). The structures of 3 (R = CH2CH2SMe), 4 (R = CH2Ph), 7 (M = Ir) and 21 (M = Pd, R = H) have been determined by X-ray diffraction


N,N-Dimethyl-C-phenylglycinemethylester reacts with Pd(OAc)2 in acetic acid to give the orthopalladated, acetato bridged complex 1. Treatment of 1 with sodium halide affords the chloro, bromo, and iodo bridged compounds [Me2NC(H)(CO2Me)C6H4PdX]2 (2a -c) (X = halide). From 2a and 1,1′-bis(diphenylphosphino)ferrocene the phosphine bridged trinuclear complex 3 is obtained. Substitution of the amine ligand of 2a by the phosphino group is observed for the reaction of 2a with Ph2PC(Me)C(Me)PPh2. Insertion of 2,6-dimethyl-phenylisocyanide, CO, alkyl-vinyl-ketones, and diphenylacetylene into the Pd-C bond o f 2a -c provides the orthosubstituted organic and organometallic derivatives of phenylglycine 6a -c, 7, 8a -b and 9a -c. The crystal structures of 1, 4a, 6a, 7 and 9a were determined by X-ray diffraction.

Lithiation of 1,2-dichloro- or 1,2,3-trichloroferrocene with lithium tetramethylpiperidinide, followed by transmetallation with ZnCl2 and Pd(II)-catalyzed coupling with 2-bromopyridine, yield the pyridylferrocenes [CpFe{C5H2-nCl2+n(2-C5H4N)}] (2a, b, n=0 or 1) as brown oils of low stability. Recrystallization of 2b produced a small number of X-ray quality crystals, which could be shown to have the proposed constitution. However, from the recrystallization solution of 2a a few crystals precipitated whose X-ray structure determination identified them as a metal-free phosphonium ylide {C5HCl2(2-C5H4N)(PPh3)} (3)

Recrystallization of silver pentacyanocyclopentadienide Ag[C5(CN)5] from N,N-dimethylformamide (DMF) gives the polymeric 1:1 complex [Ag{C5(CN)5}(DMF)] (1). The Ag+ cation is coordinated by three N atoms of three different [C5(CN)5]- anions and two O atoms of two DMF molecules. Each [C5(CN)5]- is coordinated via three neighboring CN groups to three different Ag+ ions, while each DMF molecule bridges two Ag+ ions via its O atom. Treatment of NiCl2 6H2O, CoCl2 6H2O or ZnCl2 with Ag[C5(CN)5] in DMF gives the DMF complexes [M(DMF)6][C5(CN)5]2 (M=Ni, 2; Co, 3; Zn, 4). The complexes 2 and 3 were characterized by X-ray diffraction and show octahedral [M(DMF)6]2+ cations with O-coordinated DMF molecules. The [C5(CN)5]- anions show ideal pentagonal symmetry

The 1,1-dithiolates Ph2C═N-C(CO2Et)═CS2 2− and Me2NC(CO2Et)═CS2 2− from diphenylmethylene glycine ethylester or N,N-dimethylglycine ester and CS2 react under basic conditions with chlorophosphine compounds of Pd(II), Pt(II) and gold(I) to give the complexes Ph2C═N-C(CO2Et)═CS2ML2, Me2N-C(CO2Et)═CS2ML2 (M = Pd, Pt; L = PPh3, 2L = Ph2PCH2CH2PPh2) and Ph2C═N-C(CO2Et)═CS2(AuPPh3)2, and Me2N- C(CO2Et)═CS2(AuPPh3)2.

The structures of the palladium complex Ph2C═N-C(CO2Et)═CS2Pd(PPh3)2 and of diphenylmethylene- L-alanine ethylester were determined by X-ray diffraction. Besides this S,S-complex also the (less stable) S,O-isomer could be detected.