Platinum(II) iodide complexes with propan-1-amine

Summary Thecis-[PtPra₂I₂],trans-[PtPra₂I₂], [PtPra₃I]I, [PtPra₄]I₂ and [PtPra₄]I₂ · 2H₂O (Pra = propan-1-amine) complexes have been prepared and characterized by elemental analyses, i.r. and¹H n.m.r. spectra and t.g., d.t.g. and d.t.a. measurements. Thermal degradation of the 13 and 14 complexes yieldstrans-[PtPra₂I₂] as an intermediate, whereascis-[PtPra₂I₂] isomerizes totrans without decomposition. The¹H n.m.r. spectra of the 12 and 14 species in deuteriated solvents are characteristic of the stoichiometry and geometry, whereas the spectra of [PtPra₃I]I indicate a general instability of this complex in solution, owing to easy decomposition to give trans-[PtPra₂I₂].     

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.     

The molecular structure of dibutylbis(2-pyridinethiolato-5-ethyl ester)tin(IV), [SnBu2(TNEE)2]

The crystal structure of [SnBu₂(TNEE)₂], (HTNEE=5-ethyl ester of 2-mercaptopyridine-5-carboxylic acid) has been determined by X-ray single crystal diffraction study. The crystal is triclinic, space groupP,a=10.042(1),b=18.421(2),c=7.979(1) Å, =98.7(1), =107.3(1), =87.7(1)^o,V=1393(1) ų, and Z=2 The tin center is coordinated to two butyl groups and to the nitrogen and the sulfur atoms of two ligand molecules in a very distorted trapezoidal bipyramid.     

Palladium and platinum dihalide complexes with dl-selenomethionine

Palladium and platinum dihalides react with dl-selenomethionine (sem), yielding the complexes [M(sem)X2](M=Pd,X=Cl or Br;M=Pt,X=Cl) and, in the presence of N,N-dimethylformamide (dmf), the species [M(sem)X2]·dmf (M=Pd, X=I; M=Pt, X=Cl, Br or I). The complexes were characterized by i.r. and proton n.m.r. spectroscopy and by thermogravimetric analysis, and their properties were compared with those of the dl-methionine analogues [M(Met)Cl2] and [Pt(Met)Cl2]·dmf. On the basis of n.m.r. data in deuteriated dimethyl sulfoxide, the platinum complexes undergo ligand rearrangement to form [Pt(sem)2]2+ moieties whereas the solvent does not seem to interact with the palladium coordination sphere, which contains the chelated N, Se ligand.     

Platinum(II) halide complexes with propan-1-amine

Summary The complexescis-[PtPra₂X₂],trans-[PtPra₂X₂], [PtPra₃X]X, [PtPra₄]X₂ and [PtPra₄]X₂ · 2H₂O, where Pra= propan-1-amine and X=Cl or Br, have been prepared with good yields and characterized by thermal analysis and i.r. and¹H n.m.r. spectroscopy. The best methods to obtain the pure products are discussed. The TG and DTA data are reported for all the complexes; in particular the thermal degradation of the 13 and 14 bromo-derivatives allows to isolate the intermediatetrans-[PtPra₂Br₂]. The i.r. spectra are characteristic of geometry and stoichiometry, as the¹H n.m.r. spectra ofcis-[PtAm₂Br₂],trans-[PtAm₂Br₂], [PtAm₃Br]Br and [PtAm₄]Br₂ (Am=propan-1-amine or hexan-1-amine) in deuteriated benzene, acetone and chloroform.     

Complexes of uranium and thorium tetrachlorides and uranyl nitrate withN-methyl-N-ethylO-ethylcarbamate

Summary TheN-methyl-N-ethylO-ethylcarbamate ligand (L) has been synthesized and its UCl₄4·2 L, UO₂(NO₃)₂ · 2 L and ThCl₄·3L complexes isolated. In addition, the UCl₄4-2L complex (where L=N,N-diethylO-ethylcarbamate) is described. From the i.r. spectra, it is clear that the ligands bind to the metal through the carbonyl oxygen atom. The¹H n.m.r. spectra of ligands and complexes are reported and discussed.     

Palladium(II) halide complexes with dithioesters derived from sarcosine

Summary The compounds EtO₂CCH₂(Me)NCS₂R (R = Me, ESDTM; R = Et, ESDTE) were prepared from sarcosine ethyl ester hydrochloride, CS₂ and alkyl iodide in EtOH-H₂O. These ligands react with palladium halides in benzene to yield the benzene solvates [Pd(ESDTR)X₂]·nC₆H₆ (R = Me or Et; X = Cl or Br; n < 1), in which the dithioester molecule coordinates through both sulphur atoms. Ligands and complexes have been characterized by i.r. and ¹H n.m.r. spectroscopy and by thermal analysis (t.g., d.t.g. and d.t.a.). The low stability of the adducts in both solution and solid phase is discussed on the basis of proton n.m.r. spectra. Thermal degradation of the 1∶1 complexes has been examined up to 1000° C. The first decomposition step involves release of alkyl halide to form the [Pd(ESDT)X] _n (X = Cl or Br) intermediates, which successively decompose, finally giving palladium.     

Rhodium(III) halide complexes with sulphur donors. The crystal structure ofmer-tris(o-ethylthiocarbamate)-trichlororhodium(III)acetone(1/1)

Summary The complexes [Rh(TC)₃Cl₃] · Me₂CO and [Rh(TC)₃X₃] · 0.5 Me₂CO (TC=O-ethylthiocarbamate; X=Br or I) have been prepared and characterized by i.r. and¹H n.m.r. spectroscopy.The crystal structure of [Rh(TC)₃Cl₃] · Me₂CO has been determined by x-ray diffractometer data and refined to R=0.040. Crystals are monoclinic, space group P2₁, with a=9.101(5), b=15.785(8), c=8.776(5) Å, and =103.00(3)°; Dx=1.57 gcn^–3 for Z=2. The complex is monomeric with octahedral Rh. Relevant distances are Rh-Cl (trans to one another) 2.354(2) and 2.353(2) Å, Rh-Cl (trans to S) 2.388(2) Å; Rh-S (trans to one another) 2.376(3) and 2.369(3) Å, Rh-S (trans to Cl) 2.332(3) Å. There is intramolecular, and possibly intermolecular, hydrogen bonding in the structure.