Cis - and trans -influences in [PtCl 2 (SPh 2 ) 2 ] (original) (raw)
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Journal of Organometallic Chemistry, 1996
Two methods of phenylation of platinum(II) complexes are described, one by heating [PtCl(dms)3](BPh 4) and another starting from triphenyltin hydride and ['PtC12(dms)2], dms = dimethylsulfide. Two different polymorphs of trans-[PtPhCl(dms) 2] are obtained, one monoclinic and one triclinic. The monoclinic form contains two crystallographically different complexes. The main difference between the molecular geometries in the po!ymorphs is the orientation of the dms ligands. Distances found are Pt-CI, 2.403-2.420; Pt-S, 2.279-2.298 and Pt-C, 1.99-2.00 A. A comparison of some Pt-CI bond distances obtained from the literature reveals that the trans influence increases in the following order: C1 < S < Sn, P < C, H < Si. -328X(95)06103-7 trans influence on a bond distance may dominate over other factors, such as packing forces and cis influence . In trans-[PtC1X(dms)2], the Pt-CI distances are 2.30 and 2.31 /~ for X = C1 and dins, respectively . Pt(II) is a soft metal acceptor and thus prone to form more strong bonds with soft donor atoms than with hard ones. This will affect the bond in trans position, and it is anticipated that the trans influence is correlated to the hard/soft properties of the donor atoms involved. Therefore we have tried to synthesize complexes with X ligands having the soft donor atoms C or Sn. This paper reports two synthetic routes for the complex trans-[PtPhCl(dms)2] and the crystal structures of two polymorphs.
Journal of Molecular Structure: THEOCHEM, 2004
A series of different ligands, X, varying from the neutral H 2 O to the strong s donor, SiH 3 2 , has been taken in the complex [PtClX(dms) 2 ] in an effort to rationalize the trans influence of these ligands on the Pt -Cl bond. Several factors have emerged from this study. The first is that the Pt-Cl bond length is highly sensitive to the nature of the ligand opposite to it. There exists a linear relationship between the Pt -Cl bond length and the hardness of the ligand, besides various other linear relationships, such as those with the partial charge densities on the Pt and Cl atoms, the population of the platinum and chlorine orbitals, etc. Some observations regarding the relative strengths of the Pt -S bonds for dms and dmso ligands have also been made. q
Australian Journal of Chemistry
Two complexes, namely, chloro[N-(2-aminoethyl)-N-(2-ammonioethyl)ethane-1,2-diamine]platinum(II) chloride {[PtCl(tren+H)]Cl2} and dichloro[4,7-diaza-1-azoniacyclononane]platinum(II) tetrachloroplatinate(II)–water (1/2) {[PtCl2(tacn+H)]2[PtCl4]·2H2O}, have been prepared and structurally characterized by single-crystal X-ray diffractometry as part of a study of the nature and strength of Pt···H(–N) interactions. Crystals of [PtCl(tren+H)]Cl2 are monoclinic, space group P21/c, a 8.293(2), b 14.396(6), c 11.305(3) Å, β 107.34(2)º, Z 4, and the structure has been refined to a residual of 0.042 based on 1631 reflections. Crystals of [PtCl2(tacn+H)]2[PtCl4]·2H2O are monoclinic, space group P21/a, a 12.834(4), b 8.206(4), c 13.116(8) Å, β 93.01(4)˚, Z 2, and the structure has been refined to a residual of 0.035 based on 1974 reflections. In [PtCl(tren+H)]2+, the protonated amine forms hydrogen bonds with chloride anions and no close contacts with the metal ion. In [PtCl2(tacn+H)]+, a short ...
Inorganica Chimica Acta, 1990
The reaction of the complexes K[Pt(Me,SO)Xs] (X = Cl, Br) with MeCN in water results in the isolation of solid cis-[Pt(MezSO)(MeCN)X2] complexes. The latter complexes were characterized by the elemental analysis, IR and 'H NMR spectra and their structure was determined by the X-ray analysis. The complexes cis-[Pt(Me2SO)(MeCN)X2] are isostructural. cis-[Pt(Me,SO)(MeCN)C12] crystallizes in the triclinic space group Pi. The unit cell parameters are: a = 7.346(l), b = 8.865(l), c = 14.886(2) a, CY = 90.58(l), fl = 96.10(l), y = 87&l(2)", V = 962.9(3) A3, pcA = 2.65 g cmw3, Z = 4; bond lengths in two crystallographically independent molecules (a): pt-Cl (trans to N) 2.278(2), 2.278(2); Pt-Cl (truns to S) 2.310(3), 2.322(3), Pt-N 1.977(g), 1.956(8); Pt-S 2.216(2), 2.224(3). cis-[Pt(MezSO)(MeCN)Br2] crystallizes in the triclinic space group Pi. The unit cell parameters are: a = 7.569(l), b = 9.053(2), c = 15.014(3) 8. (Y = 90.33(l), 0 = 95.20(l), y = 87.12(l)", V = 1023.3(4) A3, pcalc = 3.08 g cme3, Z = 4; bond lengths in two crystallographically independent molecules (A) are: Pt-Br (trans to N) 2.397(2), 2.394(2), Pt-Br (Vans to S) 2.429(2), 2.427(2), F'-N 1.983(13), 1.986(14), pt-S 2.228(4), 2.233(5). Comparison of the data with those known from the literature suggests a mutual ligands influence in the cis-[Pt(Me2SO)(ligand)Xz] complexes.
Inorganic Chemistry, 2010
The relevance of cis and trans influences of some anionic ligands X and Y in cis-[PtX2(PPh3)2] and cis-[PtXY(PPh3)2] complexes have been studied by the X-ray crystal structures of several derivatives (X2 = (AcO)2 (3), (NO3)2 (5), Br2 (7), I2 (11); and XY = Cl(AcO) (2), Cl(NO3) (4), and Cl(NO2) (13)), density functional theory (DFT) calculations, and one bond Pt-P coupling constants, 1JPtP. The latter have allowed an evaluation of the relative magnitude of both influences. It is concluded that such influences act in a cooperative way and that the cis influence is not irrelevant when rationalizing the 1JPtP values, as well as the experimental Pt-P bond distances. On the contrary, in the optimized geometries, evaluated through B3LYP/def2-SVP calculations, the cis influence was not observed, except for compounds ClPh (21), Ph2 (22), and, to a lesser extent, Cl(NO2) (13) and (NO2)2 (14). A natural bond order analysis on the optimized structures, however, has shown how the cis influence can be related to the s-character of the Pt hybrid orbital involved in the Pt-P bonds and the net atomic charge on Pt. We have also found that in the X-ray structures of cis-[PtX2(PPh3)2] complexes the two Pt-X and the two Pt-P bond lengths are different each other and are related to the conformation of the phosphine groups, rather than to the crystal packing, since this feature is observed also in the optimized geometries.
Inorganic Chemistry, 2009
The relevance of cis and trans influences of some anionic ligands X and Y in cis-[PtX 2 (PPh 3) 2 ] and cis-[PtXY(PPh 3) 2 ] complexes have been studied by the X-ray crystal structures of several derivatives (X 2 = (AcO) 2 (3), (NO 3) 2 (5), Br 2 (7), I 2 (11); and XY = Cl(AcO) (2), Cl(NO 3) (4), and Cl(NO 2) (13)), density functional theory (DFT) calculations, and one bond Pt-P coupling constants, 1 J PtP. The latter have allowed an evaluation of the relative magnitude of both influences. It is concluded that such influences act in a cooperative way and that the cis influence is not irrelevant when rationalizing the 1 J PtP values, as well as the experimental Pt-P bond distances. On the contrary, in the optimized geometries, evaluated through B3LYP/def2-SVP calculations, the cis influence was not observed, except for compounds ClPh (21), Ph 2 (22), and, to a lesser extent, Cl(NO 2) (13) and (NO 2) 2 (14). A natural bond order analysis on the optimized structures, however, has shown how the cis influence can be related to the s-character of the Pt hybrid orbital involved in the Pt-P bonds and the net atomic charge on Pt. We have also found that in the X-ray structures of cis-[PtX 2 (PPh 3) 2 ] complexes the two Pt-X and the two Pt-P bond lengths are different each other and are related to the conformation of the phosphine groups, rather than to the crystal packing, since this feature is observed also in the optimized geometries.
Canadian Journal of Chemistry, 1973
The reaction of K2PtCl4 with CH3—CH=CH—CH2—OH yields the complex cis-[PtCl2((CH2=CH—CH(CH3))2O)]. The crystals are triclinic, space group [Formula: see text], a = 9.420(2) Å, b = 8.359(4) Å, c = 7.837(4) Å, α = 91.10(4)°, β = 62.13(4)°, γ = 80.80(5)°, and Z = 2. The structure, solved by standard methods, has been refined anisotropically by full matrix least-squares methods to a R factor of 0.052 by use of 2441 independent observed reflections. The complex is a monomer, where both double bonds of the diolefin ether are coordinated to the platinum atom as in Zeise's salt. The usual square planar coordination of platinum(II) is completed by two chlorine atoms. The (=CH2) groups of both double bonds are found on the same side of the coordination plane. Various possible conformations of the coordinated ligand in the complex are discussed.
Reviews in Inorganic Chemistry, 2014
This review covers almost 100 organoplatinum complexes: trimers (40 examples), tetramers (40 examples), pentamers (4 examples), hexamers (5 examples), nona-and oligomers (8 examples). Platinum is predominantly found in the oxidation states +2 and +4. A number of coordination geometries are observed, the most common being essentially square planar, especially with Pt(II), and distorted octahedral, especially with Pt(IV). The most common ligands are methyl, carbonyl, PX 3 and bis(diphenylphosphine)methane. Relationships between the Pt-Pt distances, Pt-X-Pt bridge angles, Pt-L bond distances and covalent radii of coordinated atoms are discussed. The mean Pt-Pt bond distance elongates in the order of nuclearity: 269.0 pm (trimers) < 270.5 pm (tetramers) < 271.5 pm (dimers) < 278.0 pm (oligomers). A comprehensive brief discussion on over 1600 organoplatinum complexes and over 2500 platinum coordination complexes is given. These complexes prefer to crystallize in monoclinic (53%) and triclinic (27%) crystal classes. About l0% of these 4100 plus complexes exist as isomers. It is observed that these isomers are more often stereoisomers than structural isomers and that distortion isomerism is surprisingly more common than the better known cis-trans isomerism, especially in the chemistry of Pt(II) complexes.
Inorg Chem, 1994
0 OC. Yield: 0.13 g, 40%. Anal. Calcd for CIlH18BrCr: C, 46.86; H, 6.43; Br, 28.35. Found: C, 42.89; H, 5.92; Br, 26.68. Determination of Ktc for the Equilibrium between 2 and 3. The value of K for the equilibrium [Cp*CrMeC1l2 a 2[Cp*CrMeC1] was esti-mat2 using the concentration dependence of the intensity of the characteristic EPR signal of 3 in . For a simple dimer-monomer equilibrium, where Kq = [312/[2] and [Crlto,l = [31 + 2[2], it can be shown that solving for [3] and taking the real root gives the expression (1)