Palladium(II) and platinum(II) complexes of rhodanine and 3-methylrhodanine

Summary The following palladium(II) and platinum(ll) complexes of rhodanine (HRd) and 3-methylrhodanine (MRd) have been prepared: Pd(HRd)_1.5Cl₂, Pd(HRd)₂Br₂, Pd(HRd)₂Br₂ · 0.25 EtOH, M(MRd)₂X₂ [M = Pd, X = Cl (0.25 EtOH) or Br; M = Pt, X = Cl or Br], Pd(MRd)₃Br₂, and M(MRd)₄(ClO₄)₂ (M = Pd or Pt). The ligands are coordinated to the metal through the thiocarbonylic sulphur atom. Pd(HRd)_1.5Cl₂ has presumably a structure such as (X = Cl or Br) complexes have a trans-planar coordination. Pd(MRd)₂X₂ (X = Cl or Br) complexes arecis-planar coordinated. Pd(MRd)₃Br₂ has presumably a square coordination with two MRd molecules and two CI ionscis-coordinated in the equatorial plane, and a MRd molecule and a Cl ion weakly bonded in apical position. The M(MRd)₄(ClO₄)₂ complexes have square planar coordination.Author to whom all correspondence should be addressed.     

Palladium(II) and platinum(II) halide complexes with 2,6-dimethyl-4H-pyran-4-thione

Summary 2,6-Dimethyl-4H-pyran-4-thione (DMTP) acts as a sulphur donor towards Pt^II and Pd^II halides yielding adducts of general formula [M(DMTP)₂X₂] (M=Pd or Pt; X=Cl, Br or I). When complex syntheses are performed in benzene, the solvated species [M(DMTP)₂X₂]·C₆H₆ (M=Pd or Pt; X=Cl or Br) are obtained. The compounds have been characterized by i.r. and n.m.r. (¹H and¹³C) spectroscopy and by thermogravimetric data. The adduct geometry and the influence of benzene are discussed.     

Complexes of metal ions with phosphorus or arsenic containing ligands,part XX. Chelates ofo-phenylenebis(diarylarsines) with palladium(II) and platinum(II) halides,pseudohalides and perchlorates

Summary Two ditertiaryarsines,o-phenylenebis(diphenylarsine), (pdpa) ando-phenylenebis(di-p-tolylarsine), (pdta) yield some new complexes of palladium(II) and platinum(II). These are: square planar M(pdta)X₂ · nCH₂Cl₂, [M = Pd, X = Cl, Br or NCS; M = Pt, X = Cl]; [Pt(A-A)₂] X₂ · nCH₂Cl₂, [(A-A) = pdta, X = Cl, NCS or ClO₄; (A-A) = pdpa, X=ClO₄] and [M₂(A-A)₂(NCS)₂] (ClO₄)₂ · nCH₂Cl₂, [M = Pd, (A-A) = pdta; M = Pt, (A-A) = pdpa]; distorted octahedral M(pdta)₂-X₂nCH₂Cl₂, [M = Pd, X = I; M = Pt, X = Br or I] and [Pd(pdta)₂(H₂O)₂](ClO₄)₂, and five coordinate [M(A-A)₂X] ClO₄ · nCH₂Cl₂, [M = Pd, Pt, (A-A) = pdta, X = I; M = Pt, (A-A) = pdpa, X = Br or I]. The [M₂(A-A)₂(NCS)₂] (ClO₄)₂ · nCH₂Cl₂ complexes are novel in the sense that they contain bridging thiocyanate together with ionic perchlorate. The stereochemical assignments have been made on the basis of i.r. and u.v. spectra as well as conductance data.     

Co-ordination compounds of diacetyldihydrazone and diacetylbis(monomethylhydrazone)

Summary Diacetyldihydrazone (DADH) forms only six-coordinate complexes with iron(II), cobalt(II), nickel(II) and zinc(II). In M(DADH)₂X₂ (M=Fe, X=Br or I; M=Co, X=I; M=Ni, X=Cl, Br or NCS) the ligand is chelating in the [M(DADH)₃]²⁺ cations, while in M(DADH)₂X₂ (M=Co, X=Cl or Br; M=Ni, X=Cl or Br) the ligand is probably bridging and bidentate. Diacetylbismonomethylhydrazone (DAMH), by contrast, forms predominantly tetrahedral complexes M(DAMH)X₂ (M=Fe or Co, X=Cl or Br; M=Ni, X=Br; M=Co, X=NCS; M=Zn, X=Cl, Br or NCS) and some octahedral complexes M(DAMH)₂X₂ (M=Co, X=NCS; M=Ni, X=Br). The i.r. spectra, electronic spectra and magnetic moments of the complexes are discussed.     

Mixed dimethyl sulfoxide-thiocarbamic ester complexes of platinum(II) halides

Summary The platinum(II) halidecis-[Pt(DMTC)(DMSO)X₂] andcis-[Pt(DETC)(DMSO)X₂](X=Cl or Br; DMSO=dimethyl sulfoxide; DMTC=EtOSCN-Me₂; DETC=EtOSCNEt₂) adducts and the platinum(II) and palladium(II) halide adducts,trans-[M(DETC)₂X₂] (M=Pt or Pd; X=Cl or Br), have been prepared. The complexes were characterized by i.r., and¹H and¹³Cn.m.r. spectroscopy. Both DMTC and DETC coordinate through the sulphur atoms. The 1:2 DETC complexes present the usualtrans configuration, whereas the presence of DMSO favourscis geometry in the mixed species.     

Ring-opening reactions induced by gold(I) of five- and four-coordinate palladium(II) and platinum(II) complexes containing tripodal or linear polyphosphines

The tripodal ligands NP(3)(tris[2-(diphenylphosphino)ethyl]amine) and PP(3)(tris[2-(diphenylphosphino)ethyl]phosphine), form five-coordinate [Pd(NP(3))X]X [X = Cl (1), Br (2)], [M(PP(3))X]X [M = Pd: X = Cl (4), Br (5), I (6); M = Pt, X = Cl (7), Br (8), I (9)] and four-coordinate[Pd(NP(3))I]I (3) complexes containing three fused rings around the metal. The interaction between Au(tdg)X (tdg = thiodiglycol; X = Cl, Br) or AuI and the respective ionic halo complexes 1-9 in a 1:1 stoichiometric ratio occurs via a ring-opening reaction with formation of the heterobimetallic systems PdAu(NP(3))X(3)[X = Cl (11), Br (12), I (13)], [MAu(PP(3))X(2)]X [M = Pd: X = Cl (14), Br (15), I (16); M = Pt: X = Cl (17), Br (18), I (19)]. The cations of complexes 17 and 18 were shown, by X-ray diffraction, to contain a distorted square-planar Pt(II) arrangement (Pt(P(2)P)X) where PP(3) is acting as tridentate chelating ligand and an almost linear PAuX moiety bearing the dangling phosphorus formed in the ring-opening process. PPh(3) coordinates to Au(I) and not to M(II) when added in excess to 14 and 17. Complexes 14-17 and [Pt(P(4))](BPh(4))(2) (10) (P4=linear tetraphosphine) also react with A(I), via chelate ring-openings to give MAu(2)(PP(3))X(4) [M = Pd: X = Cl (20), Br (21), I (22); M = Pt: X = Cl (23)] and [Pt(2)Au(2)(mu-Cl)(2)(mu-P(4))(2)](BPh(4))(4) (24), respectively.     

Synthesis and characterization of Ru(III), Rh(III), Pt(IV) and Ir(III) thiosemicarbazone complexes

Ru(III), Rh(III), Pt(IV) and Ir(III) complexes of 2-furfural thiosemicarbazone as ligand have been synthesised. These complexes have the composition [M(ligand)₂X₂]X (M = Ru(III) Rh(III) and Ir(III) X = Cl and Br) and [Pt(ligand)₂ X₂] X₂ (X = Cl, Br and 1/2SO₄). The deprotonated ligand forms the complexes of the formulae M(ligand-H)₃ and Pt(ligand-H)₃Cl. All these complexes have been characterized by elemental analysis, magnetic measurements, electronic and infrared spectral studies. All the complexes are six-coordinate octahedral.     

Chelate complexes of some NNO tridentate Schiff bases with iron(II), cobalt(II), nickel(II) and copper(II)

Summary The Schiff bases a-(C₅H₄N)CMe=NNHCOR (R = Ph, 2-thienyl or Me), prepared by condensation of 2-acetylpyridine with the acylhydrazines RCONHNH₂, coordinate in the deprotonated iminol form to yield the octahedral complexes, M[NNO]₂ M = Co or Ni; [NNOH] = Schiff base and the square-planar complexes, Pd[NNO]Cl. The Schiff bases also coordinate in the neutral keto form yielding the octahedral complexes (M[NNOH]2)Z2 (M = Ni, Co or Fe; Z = C104, BF₄ or N03) and complexes of the type M[NNOH]X2 (M = Ni, Co, Fe or Cu; X = Cl, Br or NCS). Spectral and x-ray diffraction data indicate that the complexes M[NNOH]X2 (M = Ni or Fe) are polymeric octahedral, as are the corresponding cobalt complexes having R = 2-thienyl. However, the cobalt complexes Co[NNOH]X2 (X = CI or Br; R = Ph or Me) and the copper complexes Cu[NNOH]CI₂ (R = Ph, 2-thienyl or Me) are five-coordinate, while the thiocyanato complex Co[NNOH](NCS)₂ (R = 2-thienyl) is tetrahedral.     

The coordination chemistry ofN,N′-ethylenebis(2-acetylpyridine imine) andN,N′-ethylenebis(2-benzoylpyridine imine); two potentially tetradentate ligands containing four nitrogen atoms

Summary New complexes of the general formulae [ML_A(H₂O)₂]-Cl₂ (M=Ni or Cu), [ML_AX₂] (M=Co or Cu; X=Cl or Br), [NiL_ABr₂]·H₂O, [ML_A] [MCl₄] (M=Pd or Pt), [NiL_B(H₂O)₂]Cl₂·2H₂O, [ML_BCl₂] (M=Co, Ni, Cu, Pd or Pt; X=Cl or Br) and [ML_B] [MCl₄] (M=Pd or Pt), where L_A=N,N-ethylenebis(2-acetylpyridine imine) and L_B=N, N-ethylenebis(2-benzoylpyridine imine), have been isolated. The complexes were characterized by elemental analyses, conductivity measurements, t.g./d.t.g. methods, magnetic susceptibilities and spectroscopic (i.r., far-i.r., ligand field,¹Hn.m.r.) studies. Monomeric pseudo-octahedral stereochemistries for the Co^II, Ni^II and Cu^II complexes andcis square planar structures for the compounds [ML_BX₂] (M=Pd or Pt; X=Cl or Br) are assigned in the solid state. The molecules L_A and L_B behave as tetradentate chelate ligands in the Co^II, Ni^II, Cu^II and Magnus-type Pd^II and Pt^II complexes, bonding through both the pyridine and methine nitrogen atoms. A bidentateN-methine coordination of the Schiff base L_B is assigned in the [ML_BX₂] complexes (M=Pd or Pt; X=Cl or Br). The anomalous magnetic moment values of the Co^II complexes are discussed.     

The Fourier transform Raman spectra of a series of platinum(II), palladium(II) and gold(III) square-planar complexes

The Fourier transform Raman spectra of solid samples and some D₂O solutions, of complexes of formula K_nMX₄, M = Pt(II), Pd(II), and Au(III); X = Cl and Br are reported. It was found that the spectra of the tetrabromides contain more bands than the corresponding tetrachlorides; this indication that the two halides have different crystal structures is discussed. Fourier transform Raman spectra of M(NH₃)₄Cl₂ M = Pt(II), and Pd(II), trans- and cis-Pt(NH₃)₂Cl₂ (i.e. the pharmaceutical product “cis-platin”), and trans-Pd(NH₃)₂X₂, X = Cl and Br are also reported here and the significance of the spectra discussed. Although many of these spectra have been reported earlier the quality of the new Fourier transform data is superior to that in the literature.     

Nickel(II) and copper(II) complexes of 2,5-dimethyl-1,3,4-thiadiazole

Summary Nickel(II) and copper(II) complexes of 2,5-dimethyl-1,3,4-thiadiazole Ni(DTZ)X₂ (X = Cl or Br) and M(DTZ)₂X₂ (M = Ni, X = 1 or N03; M = Cu, X = Cl, Br or NO₃) have been prepared. The i.r. spectra show that in all the complexes the ligand is N,N- or N-bonded to the metal while the sulfur atom does not participate in coordination, and that the halide ions are coordinated forming terminal M-X bonds. The NO ₃ ^- group is coordinated in both the nitrato complexes. Magnetic moments of 3.07–3.29 B.M. for the nickel(II) and 1.86–1.92 B.M. for the copper(II) complexes were observed. The Ni(DTZ)X₂ complexes have a pseudo-tetrahedral [N₂X₂] coordination with N,N-bridging ligand molecules. The Ni(DTZ)₂X₂ and Cu(DTZ)₂X₂ complexes, with predominantly monodentate ligand, involve six-coordinate metal atoms with strong equatorial [N₂X₂] bonds and weaker axial bonds.Author to whom all correspondence should be directed.     

Nickel(II)- und Kobalt(II)-Komplexe des trans-2-Äthylmercapto-cyclohexyl-phenylphosphins

Preparation and properties of nickel(II) and cobalt(II) chelates of the bidentate ligand trans-2-ethylthio-cyclohexyl-phenylphosphine (ÄMCPP) are described. Three types of nickel(II) complexes have been obtained from ÄMCPP: the four-coordinated, square planar [Ni(ÄMCPP)₂]X₂ (X = J, Br, ClO₄); five-coordinated [Ni(ÄMCPP)₂X]X (X = Cl, NCS), [Ni(ÄMCPP)₂X]BPh₄ (X = Cl, NCS) and the octahedral [Ni(ÄMCPP)₂Cl₂]. Cobalt(II) forms tetrahedral 1.1-[Co(ÄMCPP)X₂] (X = Br, Cl) and 1.2-Co(ÄMCPP)₂X₂(X = Br, Cl, NCS) complexes. All compounds were characterized by electronic reflectance and absorption spectra, conductivity and magnetic measurements.     

Zinc(II), cadmium(II) and mercury(II) complexes of 4,6-dimethyl-pyrimidine-2(1H)-one

The following zinc(II), cadmium(II) and mercury(II) complexes of 4,6-dimethylpyrimidine-2(1H)-one (L) have been prepared and investigated by conductometric,IR and Raman methods: MX₂L₂ (M = Zn, X = Cl, Br(CHCl₃, I(CHCl₃, CF₃COO; M = Cd, X = Cl, Br CF₃COO; M = Hg, X = Cl, CF₃COO), Cd₂I₄L₃, Hg₃X₆L₂ (X = Cl, Br), Hg₃X₆L₄(X = Br, I), MX₂L₄·6H₂O (M = Zn, Cd, X = CIO₄, BF₄; M = Hg, X = CIO₄. The ligand is principally bonded through the unprotonated nitrogen atom and in some complexes also through the carbonylic oxygen atom. The zinc halide complexes are tetrahedrally coordinated, the trifluoroacetate ion is coordinated as a monodentate ligand.     

Thermal and structural properties of coordination compounds of 2-mercapto-1-methylimidazole with palladium(II) and platinum(II)

Complexes of 2-mercapto-1-methylimidazole (TMZ) with Pd^II and Pt^II of the general formula M(TMZ)_nX₂ (whereM=Pd, Pt andX=Cl, Br, I or SO₄ andn=2 or 4) were obtained. The thermal stabilities of the compounds were estimated by derivatographic measurements and lattice constants were estimated from their X-ray powder diffraction patterns.     

Complexes of N-methyl-4-mercaptopiperidine with some metal ions

Complexes of N-methyl-4-mercaptopiperidine in its zwitterionic form with Co(II) and Zn(II) salts, and in anionic form with Cu(I) and Ag(I) salts have been prepared. Stoichiometry of the complexes, Co(HRS)₂COX₄ (X = Cl and Br), Co(HRS)₂X₂ (X = ClO₄, NO₃), Co(HRS)₃X₃ (X = NO₃, ClO₄), Zn(HRS)₂ZnX₄ (X = Cl and Br), Zn(HRS)₂(NO₃)₂, Ag(RS) and Cu(RS), have been established by chemical analysis. The solid complexes have been further characterized by IR and electronic spectra measurements.     

Ni(II), Pd(II) and Pt(II) complexes of PNP and PSP tridentate amino-phosphine ligands

The ligands D((CH(2))(2)NHPiPr(2))(2) (D = NH 1, S 2) react with (dme)NiCl(2) or (PhCN)(2)MCl(2) (M = Pd, Pt) to give complexes of the form [D((CH(2))(2)NHPiPr(2))(2)MX]X (X = Cl, I; M = Ni, Pd, Pt) which were converted to corresponding iodide derivatives by reaction with Me(3)SiI. Reaction of 1 or 2 with (COD)PdMeCl affords facile routes to [κ(3)P,N,P-NH((CH(2))(2)NHPiPr(2))(2)PdMe]Cl (8a) and [κ(3)P,S,P-S((CH(2))(2)NHPiPr(2))(2)PdMe]Cl (9a) in high yields. An alternative synthetic approach involves oxidative addition of MeI to a M(0) precursor yielding [κ(3)P,N,P-HN(CH(2)CH(2)NHPiPr(2))(2)NiMe]I (10), [κ(3)P,N,P-HN(CH(2)CH(2)NHPiPr(2))(2)MMe]I (M = Pd 8b Pt 11) and [κ(3)P,S,P-S(CH(2)CH(2)NHPiPr(2))(2)MMe]I (M = Pd 9b, Pt 12). Alternatively, use of NEt(3)HCl in place of MeI produces the species [κ(3)P,N,P-HN(CH(2)CH(2)NHPiPr(2))(2)MH]X (X = Cl, M = Ni 13a, Pd 14a, Pt 16a). The analogs containing 2; [κ(3)P,S,P-S((CH(2))(2)NHPiPr(2))(2)MH]X (M = Pd, X = PF(6)15: M = Pt, X = Br, 17a, PF(6)17b) were also prepared in yields ranging from 74-93%. In addition, aryl halide oxidative addition was also employed to prepare [κ(3)P,N,P-HN(CH(2)CH(2)NHPiPr(2))(2)MC(6)H(4)F]Cl (M = Ni 18, Pd 19) and [κ(3)P,S,P-S((CH(2))(2)NHPiPr(2))(2)Pd(C(6)H(4)F)]Cl (20). Crystal structures of 3a, 4a, 5a, 6a, 8a, 9a, 14b and 16b are reported.     

N-aminorhodamne complexes of palladium(II), palladium(IV) and platinum(II)

Summary TheN-aminorhodanine (L) complexes: PdLX, (X = Br or I), ML_1.5Cl₂ (M = Pd or Pt), PtL₂X₂ (X = Br, I or ClO₄), PdL₃(ClO₄)₂, PdL_1.5Cl₄ and PdL₃(ClO₄)₄ have been prepared and investigated. The ligand is bonded to the metal ion through the aminic nitrogen atom as monodentate or through this atom and the thiocarbonylic sulphur atom when it acts as chelating or bridging ligand. The carbonylic oxygen atom is never coordinated.     

Cobalt(II), nickel(II) and copper(II) with 2-substituted benzimidazole complexes

Summary Complexes of stoichiometries M(Acbim)₂X₂·nH₂O and M(Bzbim)₂X₂·nH₂O (M = Co, Ni or Cu; Acbim = 2-acetylbenzimidazole, Bzbim = 2-benzoylbenzimidazole; X = Cl, Br, NO₃ or ClO₄; n = 0, 1 or 2) have been prepared and characterised by spectroscopic and physicochemical methods. The ligands coordinate through carbonyl oxygen and tertiary nitrogen.     

镍(II)、钯(II)、铂(II)-环戊基苯基膦配合物的合成及表征

合成了十五种配合物MX~2[(C~5H~9)~nPPh~3-n]~2系列, 其中M=Ni, X=Cl, Br,I; M=Pd, Pt, X=Cl; 且C~5H~9代表环戊基, n=1, 2, 3。通过元素分析、远红外光谱及紫外光谱确定了这些配合物的化学组成和空间构型。讨论了不同配体对配合物结构的影响。     

Novel chelate ring-opening induced by silver(I) of five-coordinate palladium(II) and platinum(II) complexes containing tripodal polyphosphines

The ionic complexes [Pd(NP 3)X]X [NP 3 = tris[2-(diphenylphosphino)ethyl]amine, X = Cl (1), Br(2)] and [M(PP 3)X]X [PP 3 = tris[2-(diphenylphosphino)ethyl]phosphine, M = Pd, X = Cl (3), Br(4); M = Pt, X = Cl (5), Br (6)] contain square pyramidal (1, 2) and trigonal bipyramidal (3- 6) cations with three fused chelate rings to M and one M-X bond. By addition of AgX salts (X = Cl, Br, NO 3) an unexpected ring-opening reaction occurs with formation of the heteronuclear species PdAg(NP 3)X 3 [X = Cl (7), Br (8)], MAg(PP 3)X 3 [M = Pd, X = Cl (9), Br (10), NO 3 (13);M = Pt, X = Cl (11), Br (12), NO 3 (14)]. The complexes have been characterized in the solid state and solution. The X-ray crystal structures of 9 and 13 reveal a distorted square-planar arrangement to Pd(II) that is coordinated to three P of PP 3 (the central and two terminal atoms) and to one chloride (9) or one oxygen atom of NO 3 (13). The resultant dangling phosphorus of the ring opening is bound to Ag(I) that completes the three- [PAgCl 2 ( 9)] and four-coordination [PAg(ONO 2)(O 2NO) (13)] through the donor atoms of the anions with the nitrates in 13 unusually acting as both mono- and bidentate ligands. Complexes 7, 8, 10, and 11 undergo oligomerization in solution. Complex 10 oligomerizes giving rise to the ionic compound [Pd 4Ag 2(PP 3) 2 Br 9]Br ( 10a) whose X-ray crystal structure indicates the presence of cations with a Pd(mu-Br) 3Pd unit that connects via bromide bridges two BrPdP 2PPAg Br 2 fragments containing distorted square-planar and trigonal-planar Pd(II) and Ag(I) centers, respectively. The palladium(II) metal centers in the central unit afford the five-coordination (PdBr 5) with a distorted trigonal bipyramidal geometry. The ionic system [Pt 2Ag 2(PP 3) 2 Cl 5]Cl (11a) consists of chloride anions and heteronuclear monocations. The X-ray crystal structure reveals that the cations contain two distorted square-planar ClPtP 3 units bridged by one PAgCl(mu-Cl) 2AgP fragment that is bearing tetrahedral (PAgCl 3) and trigonal planar PAgCl 2 silver(I) centers. Further additions of the corresponding AgX salts to complexes 7- 14 did not give rise to any new ring-opening reaction.