Cis‐ and trans‐influences in [PtCl2(SPh2)2]

Both cis‐ and trans‐di­chloro­bis­(di­phenyl ­sulfide)­platinum(II), [PtCl₂(C₁₂H₁₀S)₂], crystallize as mononuclear pseudo‐square‐planar complexes. In the cis compound, the Pt—Cl distances are 2.295 (2) and 2.319 (2) Å, and the Pt—S distances are 2.280 (2) and 2.283 (2) Å. In the trans compound, Pt is located on a centre of inversion and the Pt—Cl and Pt—S distances are 2.2786 (15) and 2.3002 (12) Å, respectively.     

Trans Influence of Triphenylstibine: Crystal Structures of cis‐[PtBr2(SbPh3)2], trans‐[PtBr(Ph)(SbPh3)2], [NMe4][PtBr3(SbPh3)], and cis‐[PtBr2(SbPh3)(PPh3)]

The work reports the unexpected reaction of diphenyldibromo antimonates (III) with PtCl₂ and cis‐[PtCl₂(PPh₃)₂]. The reaction gives triphenylstibine containing Pt^II complexes viz. cis‐[PtBr₂(SbPh₃)₂] ( 1 ), trans‐[[PtBr(Ph)(SbPh₃)₂] ( 2 ), [NMe₄][PtBr₃(SbPh₃)] ( 3 ), and cis‐[PtBr₂(PPh₃)(SbPh₃)] ( 4 ). All the complexes were characterised by elemental analyses, IR, Raman, ¹⁹⁵Pt NMR, FAB mass spectroscopy and X‐ray crystallography. A plausible mechanism via the phenyl migration is proposed for the formation of these complexes. The average Pt–Br distance in 1 is 2.456(2) Å, in 2 2.496 Å(trans to Ph) while in 3 it is 2.476 Å (trans to Sb) implying a comparable trans influence of Ph₃Sb and Ph₃P.     

trans‐Di­iodo­bis(1,3,5‐tri­aza‐7‐phosphaadamantane)­platinum(II)

The crystal structure of the title compound, trans‐[PtI₂(C₆H₁₂N₃P)₂], describes one of the few platinum(II) complexes containing two of the water‐soluble 1,3,5‐tri­aza‐7‐phosphaadamantane ligands reported to date. The complex crystallizes on an inversion centre with the most important bond lengths and angles being Pt—P 2.3128 (12) Å, Pt—I 2.6022 (6) Å, P—Pt—I 90.94 (3)° and P′—Pt—I 89.06 (3)°.     

[Bis(2‐diphenylphosphinoethyl) sulfide‐κ3P,S,P′](triphenylphosphine‐κP)platinum(II) diperchlorate acetone solvate

In the title compound, [Pt(C₁₈H₁₅P)(C₂₈H₂₈P₂S)]­(ClO₄)₂·­C₃H₆O or [Pt(PPh₃)(PSP)](ClO₄)₂·CH₃COCH₃, where PSP is the potentially tridentate chelate ligand bis(2‐di­phenyl­phosphinoethyl) sulfide, all three donor groups of the PSP ligand are coordinated to the central Pt atom, with Pt—P = 2.310 (1) Å and Pt—S = 2.343 (1) Å. The fourth coordination site is occupied by the P donor of the tri­phenyl­phosphine ligand [Pt—P = 2.289 (1) Å]. The complex cation has exact mirror symmetry, with the S atom, the Pt atom and the P atom of the PPh₃ ligand in the mirror plane. The Pt atom has a distorted square‐planar coordination geometry. A π–π interaction is present between the phenyl rings of the PPh₃ ligand and the terminal –PPh₂ group of the PSP chelate.     

Syntheses of Trifluoromethanethiolato Platinum(II) Complexes – Crystal Structures of cis‐Pt(SCF3)2(PPh3)2 and trans‐Pt(SCF3)Cl(PPh3)2

Ligand exchange reactions of cis‐PtCl₂(PPh₃)₂ and [NMe₄]SCF₃ in different ratios were studied. Depending on the stoichiometry reactions proceeded with formation of products expected for the chosen ratio, i. e. cis‐Pt(SCF₃)Cl(PPh₃)₂, cis‐Pt(SCF₃)₂(PPh₃)₂, and [NMe₄][Pt(SCF₃)₃(PPh₃)]. Starting from cis‐PtCl₂(MeCN)₂ and [NMe₄]SCF₃ and adding PPh₃ after substitution, product mixtures were dominated by the corresponding trans‐isomers. Results of the single crystal structure analyses of cis‐Pt(SCF₃)₂(PPh₃)₂ and trans‐Pt(SCF₃)Cl(PPh₃)₂ are discussed.     

trans‐Dichloro(dimethyl sulfide‐κS)(pyridine‐κN)platinum(II)

The structure of the title compound, [PtCl₂(C₅H₅N)(C₂H₆S)], consists of discrete mol­ecules in which the Pt‐atom coordination is slightly distorted square planar. The Cl atoms are trans to each other, with a Cl—Pt—Cl angle of 176.60 (7)°. The pyridine ligand is rotated 64.5 (2)° from the Pt square plane and one of the Pt—Cl bonds essentially bisects the C—S—C angle of the di­methyl sulfide ligand. In the crystal structure, there are extensive weak C—H⋯Cl interactions, the shortest of which connects mol­ecules into centrosymmetric dimers. A comparison of the structural trans influence on Pt—S and Pt—­N distances for PtS(CH₃)₂ and Pt(pyridine) fragments, respectively, in square‐planar Pt^II complexes is presented.     

cis‐[1,2‐Bis(diisopropylphosphino‐κP)‐1,2‐dicarba‐closo‐dodecaborane]dichloroplatinum(II) dichloromethane hemisolvate

The asymmetric unit of the title complex, [PtCl₂(C₁₄H₃₈B₁₀P₂)]·0.5CH₂Cl₂ or cis‐[PtCl₂{1,2‐(PⁱPr₂)₂‐1,2‐C₂B₁₀H₁₀}]·0.5CH₂Cl₂, contains one disordered solvent mol­ecule and two mol­ecules of the complex, in which each Pt^II atom displays slightly distorted square‐planar coordination geometry. The P atoms connected to the cage C atoms are coordinated to the Pt^II atom. The Pt—P distances vary slightly [2.215 (3) and 2.235 (4) Å] and the Pt—Cl distances are equal [2.348 (3) and 2.353 (5) Å].     

cis‐Di­phenyl­bis(1,3,5‐tri­aza‐7‐phospha­adamantane‐κP)platinum(II)

The structure of the title compound, [Pt(C₆H₅)₂(C₆H₁₂N₃P)₂] or [Pt(Ph)₂(PTA)₂] (where Ph is phenyl and PTA is 1,3,5‐tri­aza‐7‐phosphaadamantane), is discussed. Selected geom­etric parameters are: Pt—P = 2.2888 (16) and 2.2944 (17) Å, Pt—C = 2.052 (5) and 2.064 (6) Å, C—Pt—C = 84.6 (2)° and P—Pt—P = 99.28 (6)°. The effective cone angle for the PTA ligands was calculated as 113°.     

An organopalladium(II) compound including enolate oxy­gen‐ and sp3‐carbon‐bound 1,3‐di­methyl­barbiturate ligands: (1,2‐di­amino­ethane)­bis(1,3‐di­methyl­barbiturato)­palladium(II) 5.5‐hydrate

In the title compound, [Pd(C₆H₇N₂O₃)₂(C₂H₈N₂)]·5.5H₂O, the Pd atom is coordinated by two 1,3‐di­methyl­barbiturate anions through a deprotonated tetrahedral carbon and the enolate oxy­gen. The Pd—N bond length of 2.078 (2) Åtrans to the C atom is shorter than the Pt—N distance of 2.098 (3) Å in the Pt analog.     

A one‐dimensional chloride‐bridged PtII/PtIV mixed‐valence complex with a 4‐[(4‐hydroxyphenyl)diazenyl]benzenesulfonate counter‐ion

The title compound, catena‐poly[[[bis(ethylenediamine‐κ²N,N′)platinum(II)]‐ μ‐chlorido‐[bis(ethylenediamine)platinum(IV)]‐μ‐chlorido] tetrakis{4‐[(4‐hydroxyphenyl)diazenyl]benzenesulfonate} dihydrate], {[Pt^IIPt^IVCl₂(C₂H₈N₂)₄](HOC₆H₄N=NC₆H₄SO₃)₄·2H₂O}_n, has a linear chain structure composed of square‐planar [Pt(en)₂]²⁺ (en is ethylenediamine) and elongated octahedral trans‐[PtCl₂(en)₂]²⁺ cations stacked alternately, bridged by Cl atoms, along the b axis. The Pt atoms are located on an inversion centre, while the Cl atoms are disordered over two sites and form a zigzag ...Cl—Pt^IV—Cl...Pt^II... chain, with a Pt^IV—Cl bond length of 2.3140 (14) Å, an interatomic Pt^II...Cl distance of 3.5969 (15) Å and a Pt^IV—Cl...Pt^II angle of 170.66 (6)°. The structural parameter indicating the mixed‐valence state of the Pt atom, expressed by δ = (Pt^IV—Cl)/(Pt^II...Cl), is 0.643.     

Darstellung,Kristallstrukturen, Schwingungsspektren und Normalkoordinatenanalyse von cis‐(n‐Bu4N)2[PtX2(ox)2], X = Cl,Br, I

Synthesis, Crystal Structure, Vibrational Spectra, and Normal Coordinate Analysis of cis‐(n‐Bu₄N)₂[PtX₂(ox)₂], X = Cl, Br, I By treatment of [PtCl₆]^2— with C₂O₄^2— (ox^2—) in water cis‐(n‐Bu₄N)₂[PtCl₂(ox)₂] ( 1 ) is formed which has been isolated by ion exchange chromatography on diethylaminoethyl cellulose. Exposure of trans‐(n‐Bu₄N)₂[PtX₂(ox)₂], X = Br and I, in dichloromethane yields cis‐(n‐Bu₄N)₂[PtBr₂(ox)₂] ( 2 ) and cis‐(n‐Bu₄N)₂[PtI₂(ox)₂] ( 3 ). The crystal structure of 3 (monoclinic, space group P2₁/c, a = 19.132(1), b = 14.377(1), c = 18.099(1) Å, ß = 113.734(8)°, Z = 4) reveals, that the compound crystallizes as a racemic mixture with C₂ point symmetrical complex anions. The bond lengths in both I′‐Pt‐O^• axes are Pt‐I′ = 2.599 and Pt‐O^• = 2.052 and in the O—Pt—O axis Pt—O = 2.016 Å. The oxalato ligands are nearly plane with O—C—C—O torsion angles of 0.2—3.6°. In the vibrational spectra the PtX′ stretching vibrations are observed at 362 and 365 ( 1 ), 231 and 240 ( 2 ) and 172 and 183 cm^—1 ( 3 ). The PtO^• and PtO stretching vibrations are coupled with internal modes of the oxalato ligands and appear in the range of 400—800 cm^—1. Based on the molecular parameters of the X‐ray determination ( 3 ) and estimated data ( 1 , 2 ) the IR and Raman spectra are assigned by normal coordinate analysis. The valence force constants are f_d(PtCl′) = 2.35, f_d(PtBr′) = 2.20, f_d(PtI′) = 1.81 and f_d(PtO^•) = 2.57 ( 1 ), 2.42 ( 2 ) and 2.15 ( 3 ) and f_d(PtO) = 2.65 mdyn/Å. Taking into account increments of the trans influence a good agreement between observed and calculated frequencies is achieved. The NMR shifts are δ(¹⁹⁵Pt) = 6438.8 ( 1 ), 5988.8 ( 2 ) and 4917.3 ppm ( 3 ).     

cis‐Dichloridobis{dimethyl[3‐(9‐phosphabicyclo[3.3.1]non‐9‐yl)propyl]amine‐κP}platinum(II)

The title compound, [PtCl₂(C₁₃H₂₆NP)₂], is a rare example of a sterically bulky ligand adopting a cis geometry in a square‐planar complex. It crystallizes on a twofold rotation axis which bisects the Pt centre and the P—Pt—P′ and Cl—Pt—Cl′ angles. The ligand exhibits a random packing disorder in the N,N‐dimethylpropylamine substituent, with the two orientations refining to occupancies of 0.404 (15) and 0.596 (15). Weak intermolecular interactions between a Cl and a H atom of the ligand of a neighbouring molecule result in extended chains along the a axis. The effective cone angle for the dimethyl[3‐(9‐phosphabicyclo[3.3.1]non‐9‐yl)propyl]amine (Phoban[3.3.1]‐C₃NMe₂) ligand was determined as being in the range 160–181°, depending on the choice of atoms used in the calculations.     

Bis(8‐quinolinolato‐N,O)platinum(II) and its synthetic intermediate, 8‐hydroxyquinolinium dichloro(8‐quinolinolato‐N,O)platinate(II) tetrahydrate

Bis(8‐quinolinolato‐N,O)­platinum(II), [Pt(C₉H₆NO)₂], (I), has a centrosymmetric planar structure with trans coordination. The molecules form an inclined π stack, with an interplanar spacing of 3.400 (6) Å. 8‐Hydroxy­quinolinium dichloro(8‐quinolinolato‐N,O)­platinate(II) tetrahydrate, (C₉H₈NO)[PtCl₂(C₉H₆NO)]·4H₂O, (II), is soluble in water and is regarded as the synthetic intermediate of the insoluble neutral compound (I). The uncoordinated 8‐hydroxy­quinolinium cations and the monoquinolinolate complexes form an alternating π stack. The origins of fluorescence and phosphorescence in (II) are assigned to the 8‐hydroxy­quinolinium cation and the monoquinolinolate–Pt complex, respectively.     

syn‐Tri‐μ‐chlorido‐bis{[(R,R)/(S,S)‐2,2′‐bis(diphenylphosphino)‐1,1′‐biphenyl]hydridoiridium(III)} tetrafluoridoborate dichloromethane disolvate

In the structure of the title compound, [Ir₂Cl₃H₂(C₃₆H₂₈P₂)₂]BF₄·2CH₂Cl₂, the bimetallic cation features a confacial bioctahedral structure that is held together by three bridging chloride ions and is very close to C₂ symmetric. The hydrides are in a syn orientation (trans to the same halide bridge), and the chelating bis(phosphine) atropisomers display a racemic (R,R)/(S,S) configuration. Because of the high trans‐bond‐weakening influence of the hydride ligands, the Ir—Cl bonds trans to Ir—H [2.5262 (7) and 2.5365 (7) Å] are significantly longer than those opposite the Ir—P linkages [2.4287 (7)–2.4672 (8) Å]. The Ir—P distances vary between 2.2464 (9) and 2.2565 (8) Å. This study illustrates the usefulness of sterically demanding biaryl‐based P₂ ligands in the synthesis of halide‐bridged Ir₂ complexes, which are valuable precursors of versatile catalysts for homogeneous C=O hydrogenation.     

Bis­[tetrakis­(tri­phenyl­phosphine‐κP)silver(I)] di‐μ‐tri­fluoro­acetato‐κ4O:O′‐bis[bis­(tri­fluoro­acetato‐κO)stannate(IV)]

The crystal structure of the title compound, [Ag(C₁₈H₁₅P)₄]₂[Sn₂(CH₃)₄(CF₃CO₂)₆], consists of discrete tetrahedral cations and trans‐C₂SnO₄ octahedral dianions [C—Sn—C = 154.6 (2)°]. The dianion lies about a center of inversion and the two Sn atoms are linked unevenly by the carboxyl­ate unit [Sn—O = 2.291 (3) Å and SnO = 2.818 (3) Å].     

A one‐dimensional iodine‐bridged PtII/PtIV mixed‐valence complex,catena‐poly[[[bis­(ethyl­ene­diamine)­platinum(II)]‐μ‐iodo‐[bis­(ethyl­ene­di­amine)platinum(IV)]‐μ‐iodo] hydrogenphosphate dihydrogenphosphate iodide trihydrate]

The title compound, {[Pt^IIPt^IVI₂(C₂H₈N₂)₄](HPO₄)(H₂PO₄)I·3H₂O}_n, has a chain structure composed of square‐planar [Pt(en)₂]²⁺ and elongated octa­hedral trans‐[PtI₂(en)₂]²⁺ cations (en is ethyl­ene­diamine) stacked alternately along the c axis and bridged by the I atoms; a three‐dimensionally valence‐ordered system exists with respect to the Pt sites. The title compound also has a unique cyclic tetra­mer structure composed of two hydrogenphosphate and two dihydrogenphosphate ions connected by strong hydrogen bonds [O⋯O = 2.522 (10), 2.567 (10) and 2.569 (11) Å]. The Pt and I atoms form a zigzag ⋯I—Pt^IV—I⋯Pt^II⋯ chain, with Pt^IV—I bond distances of 2.6997 (7) and 2.6921 (7) Å, inter­atomic Pt^II⋯I distances of 3.3239 (8) and 3.2902 (7) Å, and Pt^IV—I⋯Pt^II angles of 154.52 (3) and 163.64 (3)°. The structural parameters indicating the mixed‐valence state of platinum, expressed by δ = (Pt^IV—I)/(Pt^II—I), are 0.812 and 0.818 for the two independent I atoms.     

Darstellung,Kristallstrukturen, Schwingungsspektren und Normalkoordinatenanalyse von cis‐ und trans‐(n‐Bu4N)2[PtF2(ox)2] und (n‐Bu4N)2[PtF4(ox)]

Synthesis, Crystal Structure, Vibrational Spectra, and Normal Coordinate Analysis of cis‐ and trans‐(n‐Bu₄N)₂[PtF₂(ox)₂] and (n‐Bu₄N)₂[PtF₄(ox)] By treatment of trans‐(n‐Bu₄N)₂[PtCl₂(ox)₂] and (n‐Bu₄N)₂[PtCl₄(ox)] with XeF₂ in propylene carbonate cis‐ and trans‐(n‐Bu₄N)₂[PtF₂(ox)₂] ( 1 , 2 ) and (n‐Bu₄N)₂[PtF₄(ox)] ( 3 ) are formed which have been isolated by ion exchange chromatography on diethylaminoethyl cellulose. The crystal structure of trans(n‐Bu₄N)₂[PtF₂(ox)₂] ( 2 ) (tetragonal, space group P4₂/n, a = 15.5489(9), b = 15.5489(9), c = 17.835(1)Å, Z = 4) und Cs₂[PtF₄(ox)] ( 3 ) (monoclinic, space group C2/m, a = 14.5261(7), b = 6.2719(4), c = 9.6966(9)Å, β = 90.216(8)°, Z = 4) reveal complex anions with nearly D_2h and C_2v point symmetry. The average bond lengths in the symmetrical coordinated axes are Pt—F = 1.93 ( 2 , 3 ) and Pt—O = 1.987 ( 2 ) and in the F^•—Pt—O′‐axes Pt—F^• = 1.957 and Pt—O′ = 1.977Å ( 3 ). The oxalato ligands are nearly planar with a maximum displacement of the ring atoms of 0.05 ( 2 ) und 0.01Å ( 3 ) to the calculated best planes. In the vibrational spectra the symmetric and antisymmetric PtF stretching vibrations are observed at 583 and 586 ( 2 ) and 576 and 568 cm^—1 ( 3 ). The PtF^• modes appear at 565 and 562 ( 1 ) and 560 cm^—1 ( 3 ). The PtO and PtO′ stretching vibrations are coupled with internal modes of the oxalato ligands and appear in the range of 400—800 cm^—1. Based on the molecular parameters of the X‐ray determinations ( 2 , 3 ) and estimated data ( 1 ) the IR and Raman spectra are assigned by normal coordinate analysis. The valence force constants are f_d(PtF) = 3.55 ( 2 ) and 3.38 ( 3 ), f_d(PtF^•) = 3.23 ( 1 ) and 3.20 ( 3 ), f_d(PtO) = 2.65 ( 1 ) and 2.84 ( 2 ) and f_d(PtO′) = 2.97 ( 1 ) and 3.00 mdyn/Å ( 3 ). Taking into account increments of the trans influence a good agreement between observed and calculated frequencies is achieved. The NMR shifts are δ(¹⁹⁵Pt) = 8485 ( 1 ), 8597 ( 2 ) and 10048 ppm ( 3 ), δ(¹⁹F) = —350 ( 2 ) and —352 ( 3 ) and δ(¹⁹F^•) = —323 ( 1 ) and —326 ppm ( 3 ) with the coupling constants ¹J(PtF) = 1784 ( 2 ) and 1864 ( 3 ) and ¹J(PtF^•) = 1525 ( 1 ) and 1638 Hz ( 3 ).     

trans‐Chloridobis[(Z)‐1‐imino‐1‐methoxyethane‐κN](triphenylphosphane‐κP)platinum(II) chloride monohydrate

The title compound, [PtCl(C₃H₇NO)₂(C₁₈H₁₅P)]Cl·H₂O or trans‐[PtCl{Z‐HN=C(Me)OMe}₂(PPh₃)]Cl·H₂O, crystallizes from an acetone solution of isomeric trans‐[PtCl{E‐HN=C(Me)OMe}₂(PPh₃)]Cl. The two HN=C(Me)OMe ligands show typical π‐bond delocalization over the N—C—O group [Cini, Caputo, Intini & Natile (1995). Inorg. Chem. 34 , 1130–1137] and have the unprecedented Z–anti configuration. The relative orientation of the imino ether ligands is head‐to‐tail.     

Cyano­cobalt(III) complexes of penta‐ and tetra­dentate‐coordinated macrocyclic hexa­amines

The pendent‐arm macrocyclic hexa­amine trans‐6,13‐dimethyl‐1,4,8,11‐tetra­aza­cyclo­tetra­decane‐6,13‐diamine (L) may coordinate in tetra‐, penta‐ or hexa­dentate modes, depending on the metal ion and the synthetic procedure. We report here the crystal structures of two pseudo‐octa­hedral cobalt(III) complexes of L, namely sodium trans‐cyano­(trans‐6,13‐dimethyl‐1,4,8,11‐tetra­aza­cyclo­tetra­decane‐6,13‐diamine)cobalt(III) triperchlorate, Na[Co(CN)(C₁₃H₃₀N₆)](ClO₄)₃ or Na{trans‐[CoL(CN)]}(ClO₄)₃, (I), where L is coordinated as a penta­dentate ligand, and trans‐dicyano­(trans‐6,13‐dimethyl‐1,4,8,11‐tetra­aza­cyclo­tetra­decane‐6,13‐diamine)cobalt(III) trans‐dicyano­(trans‐6,13‐dimethyl‐1,4,8,11‐tetra­aza­cyclo­tetra­decane‐6,13‐diaminium)cobalt(III) tetra­perchlorate tetra­hydrate, [Co(CN)₂(C₁₄H₃₂N₆)][Co(CN)₂(C₁₄H₃₀N₆)](ClO₄)₄·4H₂O or trans‐[CoL(CN)₂]trans‐[Co(H₂L)(CN)₂](ClO₄)₄·4H₂O, (II), where the ligand binds in a tetra­dentate mode, with the remaining coordination sites being filled by C‐­bound cyano ligands. In (I), the secondary amine Co—N bond lengths lie within the range 1.944 (3)–1.969 (3) Å, while the trans influence of the cyano ligand lengthens the Co—N bond length of the coordinated primary amine [Co—N = 1.986 (3) Å]. The Co—CN bond length is 1.899 (3) Å. The complex cations in (II) are each located on centres of symmetry. The Co—N bond lengths in both cations are somewhat longer than in (I) and span a narrow range [1.972 (3)–1.982 (3) Å]. The two independent Co—CN bond lengths are similar [1.918 (4) and 1.926 (4) Å] but significantly longer than in the structure of (I), again a consequence of the trans influence of each cyano ligand.     

Bis(4‐hydroxy­benzoato‐O)(1,4,8,11‐tetra­aza­cyclo­tetra­decane‐κ4N)nickel(II): a three‐dimensional framework built from O—H⋯O and N—H⋯O hydrogen bonds

The title compound, [Ni(C₇H₅O₃)₂(C₁₀H₂₄N₄)], contains octahedral Ni^II in a centrosymmetric trans configuration with Ni—N distances of 2.0637 (17) and 2.0699 (16) Å and an Ni—O distance of 2.1100 (14) Å. The mol­ecules are linked by a single type of O—H?O hydrogen bond [O?O 2.618 (2) Å and O—H?O 161°] into two‐dimensional sheets; a singletype of N—H?O hydrogen bond [N?O 2.991 (2) Å and N—H?O 139°] links these sheets into a three‐dimensional framework.