Walter Ponikwar

Crystal Structures of (PPh3)2Pd(N3)2, (AsPh3)2Pd(N3)2, (2-Chloropyridine)2Pd(N3)2, [(AsPh4)2][Pd2(N3)4Cl2], [(PNP)2][Pd(N3)4], [(AsPh4)2][Pt(N3)4] · 2 H2O, and [(AsPh4)2][Pt(N3)6]

The crystal structures of the monomeric palladium(II) azide complexes of the type L2Pd(N3)2 (L = PPh3 (1), AsPh3 (2), and 2-chloropyridine (3)), the dimeric [(AsPh4)2][Pd2(N3)4Cl2] (4), the homoleptic azido palladate [(PNP)2][Pd(N3)4] (5) and the homoleptic azido platinates [(AsPh4)2][Pt(N3)4] · 2 H2O (6) and [(AsPh4)2][Pt(N3)6] (7) were determined by X-ray diffraction at single crystals. 1 and 2 are isotypic and crystallize in the triclinic space group P1. 1, 2 and 3 show terminal azide ligands in trans position. In 4 the [Pd2(N3)4Cl2]2– anions show end-on bridging azide groups as well as terminal chlorine atoms and azide ligands. The anions in 5 and 6 show azide ligands in equal positions with almost local C4h symmetry at the platinum and palladium atom respectively. The metal atoms show a planar surrounding. The [Pt(N3)6]2– anions in 7 are centrosymmetric (idealized S6 symmetry) with an octahedral surrounding of six nitrogen atoms at the platinum centers. Die Kristallstrukturen von (PPh3)2Pd(N3)2, (AsPh3)2Pd(N3)2, (2-Chloropyridin)2Pd(N3)2, [(AsPh4)2][Pd2(N3)4Cl2], [(PNP)2][Pd(N3)4], [(AsPh4)2][Pt(N3)4] · 2 H2O und [(AsPh4)2][Pt(N3)6] Die Kristallstrukturen der monomeren Palladium(II)-azid Komplexe des Typs L2Pd(N3)2 (L = PPh3 (1), AsPh3 (2) und 2-chloropyridin (3)), des dimeren [(AsPh4)2][Pd2(N3)4Cl2] (4), des homoleptischen Azido-Palladats [(PNP)2][Pd(N3)4] (5) und der homoleptischen Azido-Platinate [(AsPh4)2][Pt(N3)4] · 2 H2O (6) und [(AsPh4)2][Pt(N3)6] (7) wurden rontgenographisch an Einkristallen ermittelt. 1 und 2 sind isotyp und kristallisieren in der triklinen Raumgruppe P1. 1, 2 und 3 zeigen terminale Azidliganden, die trans zueinander angeordnet sind. Die [Pd2(N3)4Cl2]2– Anionen der Verbindung 4 zeigen sowohl end-on verbruckende Azid-Gruppen als auch terminale Chlor Atome und Azidliganden. Die Azidliganden der Anionen der Verbindungen 5 und 6 liegen auf gleichsinnigen Lagen mit annahernd lokaler C4h Symmetrie an den Platin- und Palladiumatomen. Die Metall-Atome weisen eine planare Umgebung auf. Die [Pt(N3)6]2–-Anionen in 7 sind zentrosymmetrisch (nahezu S6 Symmetrie), und die Platin-Atome sind von sechs Stickstoff-Atomen oktaedrisch umgeben.

Coordinatively and Electronically Unsaturated Pentamethylcyclopentadienyliridium(III) Complexes with the Dianions of Biuret, of the Diamide of Malonic Acid and of anN-Acetyldipeptide Ester

The dianions of biuret, of the diamide of malonic acid and of N-acetyl-L-alanyl-L-alanine methyl ester give the coordinatively unsaturated 16-electron N,N′-chelate complexes [Cp*Ir[NHC(O)NHC(O)NH)] (1), [Cp*Ir[NHC(O)CH2C(O)NH)] (2) and {Cp*Ir[N(COCH3)CH(CH3)C(O)NCH(CH3)CO2Me]} (3) upon reaction with [Cp*IrCl2]2. From [(R3P)PdCl2]2 (R = Et, Ph) and biuret the complexes [(Cl)(R3P)Pd(η2-biureto)Pd]−Na+ were obtained. The X-ray structure determinations of 1 and 3 reveal that the almost planar chelate rings lie perpendicular to the Cp* ring. (© Wiley-VCH Verlag GmbH, 69451 Weinheim, Germany, 2002)

METALLORGANISCHE VERBINDUNGEN MIT N-SUBSTITUIERTEN 3-HYDROXY-2-METHYL-4-PYRIDON-LIGANDEN: QUADRATISCH-PLANARE RHODIUM(I)-IRIDIUM(I)- UND PALLADIUM(II) -KOMPLEXE

Durch Reaktion von [(OC)2MCl]2 (M = Rh, Ir) oder [(cod)RhCl]2 mit den Anionen von N-Aryl- oder N-Alkyl-substituierten 3-Hydroxy-2-methyl-4-pyridonen (O–O′) wurden Komplexe der allgemeinen Formel [L2M(O–O′)] (1–7) erhalten. Verbindungen dieses Typs konnten auch durch Umsetzung von [(OC)2Rh(acac)] (acac = Acetylacetonat) mit den entsprechenden neutralen Liganden synthetisiert werden. Der N-Phenyl-Komplex [(OC)2Rh(C12H10NO2)] (2) reagiert mit Cycloocten unter Substitution eines Carbonyl-Liganden zu [(OC)(C8H14) · Rh(C12H10NO2)] (8). Palladium-Komplexe der Formel [(R3P)Pd(O–O′)Cl] (R = Et, Bu), [(C6H4CH2NMe2)Pd(O–O′)] und [(Et3P)2Pd(O–O′)]BF4 (9–12) wurden ausgehend von [(R3P)PdCl2]2, [(C6H4CH2NMe2)PdCl]2 oder [(Et3P)PdCl2] dargestellt. Die Strukturen der N-Methyl-Verbindungen [(OC)2Rh(C7H8NO2)] (1) und [(Ph3P)Pd(C7H8NO2)Cl] (9) wurden durch Einkristall-Rontgenstrukturanalysen bestimmt. Organometallic Compounds with N-substituted 3-Hydroxy-2-methyl-4-pyridone Ligands: square planar Rhodium(I), Iridium(I), and Palladium(II) Complexes Reactions of [(OC)2MCl]2 (M = Rh, Ir) or [(cod)RhCl]2 with the anions of N-Aryl or N-Alkyl substituted 3-hydroxy-2-methyl-4-pyridones (O–O′) yield complexes of the general formula [L2M(O–O′)]. Compounds of this type are also available from reactions of [(OC)2Rh(acac)] with the corresponding neutral ligands. Substitution of one carbonyl-ligand of the N-phenyl complex [(OC)2Rh(C12H10NO2)] (2) with cyclooctene affords [(OC)(C8H14)Rh(C12H10NO2)] (8). The palladium complexes [(R3P)Pd(O–O′)Cl] (R = Et, Bu), [(C6H4CH2NMe2) · Pd(O–O′)] and [(Et3P)2Pd(O–O′)]BF4 (9–12) were synthesized from [(R3P)PdCl2]2, [(C6H4CH2NMe2)PdCl]2 or [(Et3P)PdCl2]. The structures of the N-methyl compounds [(OC)2Rh(C7H8NO2)] (1) and [(Ph3P)Pd(C7H8NO2)Cl] (9) were determined by single crystal X-ray diffraction.

Pseudohalogeno-Metallverbindungen. LXXVI Molekülstruktur von Tetrafulminatomercurat(II), [Hg(CNO)4]2–

Pseudohalogeno Metal Compounds. LXXVI Molecular Structure of Tetrafulminatomercurate, [Hg(CNO)4]2– Crystals of [AsPh4]2[Hg(CNO)4] contain [AsPh4]+ cations and [Hg(CNO)4]2– anions. The tetrafulminatomercurate ion forms a slightly distorted tetrahedron with linear fulminate ligands. In the crystal the [Hg(CNO)4]2– anions are separated by the AsPh4+ cations which explains the thermal stability of this compound.

DFT Calculations of the Structures of Various Isomers (cis/trans) of [(CH3)(PH3)M-NH2-CH2-C(O)-O] and [(Cl)(PH3)M-NH2-CH2-C(O)-O] Complexes with M = Ni, Pd and Pt

The structural parameters of the following neutral complexes [(CH3)(PH3)M-NH2-CH2-C(O)-O] and [(Cl)(PH3)M-NH2-CH2-C(O)-O], M = Ni, Pd, Pt (P and N in cis and trans position) were computed at the density functional BPW91 level of theory using a 6-31++G(2d,p) basis set for H, C, N, O, P, Cl and Ni, and quasi-relativistic core potentials for Pd (ECP28MWB) and Pt (ECP60MWB) employing a (8s7p6d)/[6s5p3d] valence basis set. The structures were fully optimised without any symmetry constraints and were found to represent true minima (number of imaginary frequencies, NIMAG= 0). In the series ofmethyl complexes for the Ni and the Pd complexes, the trans isomers were found to be slightly more stable than the cis isomers by 1.9 (Ni) and 0.6 (Pd) kcal mol-1. In the case of the Pt complex, both isomers were computed to be essentially identical in their total energy with the cis isomer being only 0.25 kcal mol-1 more stable than the trans isomer. However, in the chloro series, the trans isomers were found to be more favourable than the cis isomers in all cases by 9.7 (Ni), 7.5 (Pd) and 6.5 (Pt) kcal mol-1. This finding is in perfect accord with the experimental data for a series of palladium and platinum complexes of the type Cl(R3P)M(N,O-chelate) for which the trans-P-M-N structure has been determined by X-ray diffraction. These complexes crystallize obviously as the thermodynamically stable trans isomers.

Struktur von Hexafulminatocobaltat(III), [Co(CNO)6]3–

Pseudohalogeno Metal Compounds. LXXVII. Structure of Hexafulminatocobaltate(III), [Co(CNO)6]3– In the crystal of [AsPh4]3[Co(CNO)6] the hexafulminatocobaltate(III) anion forms an ideal octahedron with linear C≡N–O ligands and with relatively short cobalt-carbon bonds (Co–C 191 pm). In the crystal the [AsPh4]+ cations “dilute” the energy rich anions.

Metallkomplexe von biologisch wichtigen Liganden, CXXIX [1]. Palladium(II)-und Platin(II)-Komplexe von 4,4-disubstituierten Oxazolonen und C2-symmetrischen Bis(oxazolonen) Metal Complexes of Biologically Important Ligands, CXXIX [1]. Palladium(II) and Platinum(II) Complexes of 4,4-Disubstituted Oxazolones and of C2-Symmetric Bis(oxazolones)

Abstract 4-Benzyl-4-methyl-2-phenyl-5(4H)-oxazolone (1) forms with the chloro bridged compounds [R3PMCl2]2 (M = Pt, Pd) the complexes Cl2Pt(PR3)(l) (R = Et, nBu) and Cl2Pd(PEt3)(l). The enantiomeric pure C2-symmetric CMe2 bridged bis(oxazolones) 5 and 6 have also been employed which give with PdCl2 the chelate complexes 13 and 14. The X-ray structural determination of Cl2P d[O-C (O)-CMe2-N=C-CMe2-C=N-CMe2-C (O)-O ] (10) shows that one of the methyl group of the CMe2 bridge is located near the palladium atom. This can also be detected in the 1H NMR spectrum.

Metallkomplexe mit biologisch wichtigen Liganden, CL (1). 1,1-Dithiolato-Komplex von Palladium(II), Platin(II) und Gold(I) aus Diphenylmethylenglycinester sowie N,N-Dimethylglycinester und Schwefelkohlenstoff

The 1,1-dithiolates Ph2C═N-C(CO2Et)═CS22− and Me2NC(CO2Et)═CS22− 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.

Metallkomplexe mit biologisch wichtigen Liganden, CLI (1). Metallorganische Komplexe mit R-3-(3-Pyridyl)alaninat

Reactions of chloro bridged complexes with R-3-(3-pyridyl)alanine afford the chelate complexes LnM[NH2CH(CO2)CH2C5H4NH+]Cl− (LnM = Ph3P(Cl)Pd, (tol3P)(Cl)Pd, (Ph-pyridyl)2Ir, Cp٭(Cl)Rh, Cp٭(Cl)Ir, (p-Cymol)(Cl)Ru) with protonated pyridine substituents. An analogous Cp٭Rh complex with 3-(2-pyridyl)alaninate was also obtained. Addition of base (NaOMe) to these complexes gives dimeric and trimeric complexes with coordination of the pyridine N atom.

Metallkomplexe mit Biologisch Wichtigen Liganden, CIL [1]. Metallorganische η2-N,O-Lysinato-Komplexe / Metal Complexes Of Biologically Important Ligands, Cil [1]. Organometallic η2-N,O-Lysinato-Complexes

Abstract η2-N,O-Chelate complexes LnM[NH2CH(CO2)CH2CH2CH2CH2NH+3 Cl-] with L-lysinate in the protected ω-ammonium form (LnM = (allyl)2Rh, (2-pyridylphenyl)2Ir, (p-cymene)(Cl)Ru, (C6Me6)(Cl)Ru, (C5Me5)(Cl)Rh, (C5Me5)(Cl)Ir) were obtained from chloro bridged complexes. A heterometallic lysinate bridged complex Cp*(Cl)IrNH2CH(CO2)(CH2)4NH2Ir(Cl)Cp* is formed with Cp*(Cl)Ir(N,O-lysinate·HCl) and [Cp*RhCl2]2.