Juan Fornies

ABSTRACT Reaction between [NBu4][Pt(C6F5)3(dppm-κ1P)] and cis-[M(C6X5)2(thf)2] (M = Pt, Pd; X = F, Cl; thf = tetrahydrofuran) leads to dinuclear derivatives with dppm ligands bridging two metal centers: [NBu4][(C6F5)3Pt{μ-Ph2PCH2PPh(η2-Ph)}M(C6X5)2] [X = F, M = Pt (1), M = Pd (2); X = Cl, M = Pt (3), M = Pd (4)]. The structural characterization of complex 1 by single-crystal X-ray diffraction (orthorhombic system, space group Fdd2, with a = 26.520(7) Å, b = 83.69(3) Å, c = 13.835(5) Å, V = 30706(11) Å3, and Z = 16) reveals two square-planar platinum(II) fragments sharing a dppm ligand with a η2-phenyl−platinum interaction between a phenyl ring of the dppm ligand and one platinum center. This weak η2-phenyl−platinum interaction can be easily displaced by addition of ligands such as CO (giving complex 5), PPh3 (6), or p-toluidine (7). The structure of 5 was determined by single-crystal X-ray diffraction. It crystallizes in the monoclinic system, space group Pn, with a = 12.259(2) Å, b = 16.375(3) Å, c = 18.851(4) Å, β = 100.99(3)°, V = 3714.8 Å3, and Z = 2. The complex consists of two square-planar platinum(II) fragments with the dppm ligand acting as a conventional bridge.

ABSTRACT The reaction of cis-[Pt(C6F5)2(thf)2]1(thf = tetrahydrofuran) with a 1 : 1 molar ratio of 2-(diphenylmethyl)pyridine or tribenzylamine in CH2Cl2 resulted in displacement of the thf molecules and formation of cis-[Pt(C6F5)2{NC5H4(CHPh2)-2}]2 and cis-[Pt(C6F5)2{N(CH2Ph)3}]3 respectively. The solid-state structure of 2 has been established by X-ray diffraction methods and reveals the existence of a η2-phenyl–Pt interaction which is maintained in solution (NMR). Crystal data for 2·0.5C6H5Me: C33.5H19F10NPt, triclinic, space group P, a= 11.653(4), b= 12.345(3), c= 12.499(4)Å, α= 116.91(2), β= 104.33(2), γ= 103.41(2)°, Z= 2, R= 0.038 for 2791 unique ‘observed’ absorption-corrected reflections collected at 233 K. Complexes 2 and 3 reacted with CO yielding cis-[Pt(C6F5)2{NC5H4(CHPh2)-2}(CO)] and cis-[Pt(C6F5)2{N(CH2Ph)3}(CO)] respectively.

The alkynylation of trans-[Pt(C6F5)2(tht)2] (tht = tetrahydrothiophene) with LiCCR in diethyl ether (R = Ph, SiMe3) or THF (R = tBu) leads to novel dianionic species [trans-Pt-(C6F5)2(CCR)2] 2- (R = Ph (1), SiMe3 (2), tBu (3)) which have been isolated as tetrabutylammonium salts. Treatment of (NBu4)2[trans-Pt(C6F5) 2(CCR)2] (R = Ph, SiMe3, tBu) with 2 equiv of cationic hydride reagents of the type [trans-PtHL2(acetone)]+ (L = PPh3, PEt3) in acetone form, via a ligand replacement, simple bis(2-alkyne) trinuclear zwitterionic complexes trans,trans,trans-{[Pt(C6F5)2(- 1:2-CCR)2](PtHL2) 2} (R = Ph, L = PPh3 (4a), PEt3 (4b); R = SiMe3, L = PPh3 (5a), PEt3 (5b); R = tBu, L = PEt3 (6b)). The structure of complex 4b has been determined by X-ray diffraction methods

Reaction of [PdCl{S2P(OR)2}(PR′3)] with sodium sulfide or selenide in acetone afforded neutral trinuclear palladium(II) complexes of the type [Pd3(μ3-E)2{S2P(OR)2}2(PR′3)2] (E = S or Se; R = Et, Prn Pri, Bus, R′ = Et or Ph) in 24–42% yield. These complexes were characterized by elemental analysis, NMR (1H, 31P, 77Se) and FAB mass spectral data. The molecular structure of [Pd3(μ3-S)2{S2P(OEt)2}2(PPh3)2] (1)

... Soc., Dalton Trans., 1987, 2867 RSC Article ; (f) M. Appel, J. Heidrich and W. Beck, Chem. Ber., 1987, 120, 1087 ChemPort ; (g) PM Fritz, K. Polborn, M. Steiman and W. Beck, Chem. ... 14, A. Sebald, B. Wrackmeyer and W. Beck, Z. Naturforsch., Teil B, 1983, 38, 45 . ...

ABSTRACT The reaction of cis-[Pt(C6F5)2(thf)2]1(thf = tetrahydrofuran) with a 1 : 1 molar ratio of 2-(diphenylmethyl)pyridine or tribenzylamine in CH2Cl2 resulted in displacement of the thf molecules and formation of cis-[Pt(C6F5)2{NC5H4(CHPh2)-2}]2 and cis-[Pt(C6F5)2{N(CH2Ph)3}]3 respectively. The solid-state structure of 2 has been established by X-ray diffraction methods and reveals the existence of a η2-phenyl–Pt interaction which is maintained in solution (NMR). Crystal data for 2·0.5C6H5Me: C33.5H19F10NPt, triclinic, space group P, a= 11.653(4), b= 12.345(3), c= 12.499(4)Å, α= 116.91(2), β= 104.33(2), γ= 103.41(2)°, Z= 2, R= 0.038 for 2791 unique ‘observed’ absorption-corrected reflections collected at 233 K. Complexes 2 and 3 reacted with CO yielding cis-[Pt(C6F5)2{NC5H4(CHPh2)-2}(CO)] and cis-[Pt(C6F5)2{N(CH2Ph)3}(CO)] respectively.

ABSTRACT Heterobinuclear complexes of general formula [L(C6Cl5)3-x(C6F5)xPtAg(PPh3)][x= 2–0; L = tht (tetrahydrothiophene), PPh3 or pyridine (py)]14–21 have been prepared by treating the anionic platinum derivatives [NBu4][PtL(C6F5)x(C6Cl5)3-x] with [Ag(OCIO3)(PPh3)](molar ratio 1 : 1) in dichloromethane. The anionic [NBu4][(C6F5)4PtAgL](L = OEt2, PPh3 or tht)22–24 and [NBu4][cis-(C6Cl5)2(C6F5)2PtAg(tht)]25 have been obtained from the corresponding [NBu4]2[Pt(C6X5)2(C6X′5)2] and [Ag(OCIO3)L](molar ratio 1 : 1) in CH2Cl2–diethyl ether. The reaction between [NBu4][Pd(C6F5)3(tht)] and [Ag(OCIO3)(PPh3)] renders Ag(C6F5) and cis-[Pd(C6F5)2(PPh3)(tht)]. The salts [NBu4]2[Pt(C6Cl5)4] and [NBu4]2[Pd(C6F5)4] react with [Ag(OCIO3)(tht)] yielding [NBu4][Pt(C6Cl5)3(tht)] and [NBu4][Pd(C6F5)3(tht)], respectively. The reactions between [NBu4]2[Pt(C6F5)4] and [Ag(OCIO3)(tht)] or [Ag(OCIO3)(PPh3)](molar ratio 1:2) render in the first case complex 24 while in the second an unstable material which evolves to [(Ph3P)(C6F5)3PtAg(PPh3)]27 is obtained. The reaction between [NBu4]2[trans-PtCl2(C6X5)2](X = F or Cl) and [Ag(OCIO3)(tht)] or [Ag(tht)2]ClO4 have also been studied. The structures of [(tht)(C6Cl5)(C6F5)2PtAg(PPh3)]14, [NBu4][(C6F5)4PtAg(tht)]24 and [NBu4][cis-(C6Cl5)2PtAg(tht)]25 have been established by single-crystal X-ray diffraction studies. The complexes contain a strong Pt→Ag bond [2.650(2), 14; 2.641(1), 24; and 2.692(2)Å, 25] unsupported by covalent bridges, and short contacts between the o-F or o-Cl atoms of the C6X5(X = F or Cl) groups and the Ag atom are present. The relative strength of such contacts is discussed. Methods for the synthesis of mixed pentachloro-pentafluoro-phenyl starting complexes 1–13 have been investigated.

The reactions between (NBu4)2(C6X2O4) (X=HdihydroxybenzoquinonateX=Clchloranilate) and cis-[Pt(C6F5)2(THF)2] in 1:1 molar ratio render the mononuclear complexes [NBu4]2[Pt(C6X2O4)(C6F5)2] (X=H (1)Cl (2)) If the reaction is carried out in 1:2 molar ratio the dinuclear complexes [NBu4]2[M2(μ-C6X2O4)(C6F5)4] (M=PtX=H (3)M=PtX=Cl (4)M=PdX=H (5)M=PdX=Cl (6)) are obtained Complexes 3–6 can also be prepared by reacting C6X2O2(OH)2 with the dinuclear complexes [NBu4]2[M2(μ-C6F5)2(C6F5)4] in molar 1:1 ratio Cyclic voltammetry

New mono-and polynuclear alkynyl complexes containing phenylacetylide as a terminal or bridging ligand have been synthesized and characterized. In the mono (alkynyl) complexes, the cis or trans disposition of the two σ-C-donor ligands (C (C∨ P), σ-C⋮ CPh) around the ...

The trinuclear phosphido complexes [NBu4] 2 [(C6F5) 2M (μ-PPh2) 2M'(μ-PPh2) 2M''(C6F5) 2](M, M', M''= Pd, Pt) are described. The chemical oxidation of the homonuclear platinum derivative gives [(C6F5) 2Pt (μ-PPh2) 2Pt (μ-PPh2) 2Pt (C6F5) 2], which contains Pt in ...

ABSTRACT Complexes [NBu4][(C6F5)2Pt(μ-X)(μ-dppm)Pt(C6F5)2] (X = Cl, Br) react with AgClO4 and [Ag(OClO3)L] (L = PPh3, SC4H8), yielding different compounds depending on the silver reagent used. The reactions with AgClO4 in wet solvents lead to the syntheses of the complexes [(C6F5)2Pt(μ-X)(μ-dppm){Ag(H2O)}Pt(C6F5)2] [X = Cl (1), Br (2)] in which the existence of two Pt−Ag bonds is postulated. The reactions with [Ag(OClO3)(PPh3)] give similar complexes [(C6F5)2Pt(μ-X)(μ-dppm){Ag(PPh3)}Pt(C6F5)2] [X = Cl (3), Br (4)]. The presence of silver coordinated to the platinum atoms activates the substitution of the halogen bridge; thus, 3 reacts with water, yielding the complex [(C6F5)2Pt(μ-OH)(μ-dppm){Ag(PPh3)}Pt(C6F5)2] (5). Complex 5 can be prepared as well by reaction of [NBu4][(C6F5)2Pt(μ-OH)(μ-dppm)Pt(C6F5)2] (6) with [Ag(OClO3)(PPh3)]. Nevertheless, the reaction of [NBu4][(C6F5)2Pt(μ-Cl)(μ-dppm)Pt(C6F5)2] with the complex [Ag(OClO3)(SC4H8)] does not render the analogous complex to 3, but AgCl precipitates and [(C6F5)2Pt(μ-SC4H8)(μ-dppm)Pt(C6F5)2] (7) is formed. This different behavior depending on the ligand present in the silver complex is probably due to the ability of the tetrahydrothiophene ligand to act as a bridge. Single-crystal X-ray studies of 5 and 7 have been carried out. For 5, the existence of two Pt−Ag bonds with distances 2.791(1) and 2.832(1) Å has been confirmed. Complex 7 shows a distorted six-membered ring skeleton formed by the metal atoms, dppm ligand, and sulfur atom of the SC4H8 group. Compound 5·C7H8 (C74H46AgF20OP3Pt2) crystallizes in the monoclinic system, space group P21/n:  a = 14.360(1) Å, b = 21.590(1) Å, c = 21.585(2) Å, β = 90.85(1)°, V = 6691.3(8) Å3, Z = 4. Compound 7·1/2C6H14 (C56H37F20P2Pt2S) crystallizes in the monoclinic system, space group P21/n:  a = 22.258(6) Å, b = 11.351(3) Å, c = 22.268(5) Å, β = 106.21(3)°, V = 5402.6(16) Å3, Z = 4.

ABSTRACT The reaction between the half-sandwich cyclopentadienyl complexes [M(η5-C5Me5)Cl2(PEt3)] (M = Rh, Ir) and [cis-M′(C6F5)2(thf)2] (M′ = Pt, Pd; thf = tetrahydrofuran) affords the corresponding chloride-bridged heterobinuclear Rh,Ir/Pt,Pd complexes [(PEt3)(η5-C5Me5)M(μ-Cl)2M′(C6F5)2] (1−4). In contrast, similar reactions with the chloro-bridged binuclear compounds [{M(η5-C5Me5)Cl(μ-Cl)}2] (M = Rh, Ir) lead instead to the unexpected mixed salt complexes {Cp*M(μ-Cl)3MCp*}2[{(C6F5)2M′(μ-Cl)}2] (M = Rh, Ir; M′ = Pt, Pd) (5−8) as a result of chloride transfer. The structures of [(PEt3)(η5-C5Me5)Rh(μ-Cl)2Pt(C6F5)2] (1) and {Cp*Rh(μ-Cl)3RhCp*}2[{(C6F5)2Pd(μ-Cl)}2] (6) have been determined by X-ray diffraction analyses. The reactivity of the new chloride-bridged heterobinuclear compounds 1−4 towards the alkynylating agents [M′′(C≡CR)]n (M′′ = Cu, Ag) has also been investigated: a new type of tetranuclear product, [(PEt3)Cp*M(μ-1κCα:η2-C≡CPh)2M′′2(μ-4κCα:η2-C≡CPh)2Pt(C6F5)2] (M = Rh, Ir; M′′ = Cu, Ag) (9−12), was obtained, and fully characterized in the case of complex [(PEt3)Cp*Rh(μ-1κCα:η2-C≡CPh)2Cu2(μ-4κCα:η2-C≡CPh)2Pt(C6F5)2] (9).

ABSTRACT Reaction between [NBu4][Pt(C6F5)3(dppm-κ1P)] and cis-[M(C6X5)2(thf)2] (M = Pt, Pd; X = F, Cl; thf = tetrahydrofuran) leads to dinuclear derivatives with dppm ligands bridging two metal centers: [NBu4][(C6F5)3Pt{μ-Ph2PCH2PPh(η2-Ph)}M(C6X5)2] [X = F, M = Pt (1), M = Pd (2); X = Cl, M = Pt (3), M = Pd (4)]. The structural characterization of complex 1 by single-crystal X-ray diffraction (orthorhombic system, space group Fdd2, with a = 26.520(7) Å, b = 83.69(3) Å, c = 13.835(5) Å, V = 30706(11) Å3, and Z = 16) reveals two square-planar platinum(II) fragments sharing a dppm ligand with a η2-phenyl−platinum interaction between a phenyl ring of the dppm ligand and one platinum center. This weak η2-phenyl−platinum interaction can be easily displaced by addition of ligands such as CO (giving complex 5), PPh3 (6), or p-toluidine (7). The structure of 5 was determined by single-crystal X-ray diffraction. It crystallizes in the monoclinic system, space group Pn, with a = 12.259(2) Å, b = 16.375(3) Å, c = 18.851(4) Å, β = 100.99(3)°, V = 3714.8 Å3, and Z = 2. The complex consists of two square-planar platinum(II) fragments with the dppm ligand acting as a conventional bridge.

ABSTRACT By reacting [NBu4]2[M(C6F5)4] with cis-[M(C6F5)2(thf)2](M = Pd or Pt; thf = tetrahydrofuran) in CHCl3 the binuclear homo- or hetero-metallic complexes [NBu4]2[MM′(µ-C6F5)2(C6F5)4](M = M′= Pd or Pt; M = Pt, M′= Pd), containing bridging pentafluorophenyl groups, are obtained. Their structures have been established by 19F n.m.r. spectroscopy. The homometallic derivatives react with neutral (L) or anionic (X)– ligands yielding [NBu4][M(C6F5)3L](M = Pd or Pt; L = PPh3, CO, or ½Ph2PCH2PPh2) or [NBu4]2[MX(C6F5)3](M = Pd or Pt; X = Br), respectively. The heterometallic complex [NBu4]2[PdPt(µ-C6F5)2(C6F5)4] reacts with PPh3 or Ph2PCH2PPh2 giving rise to a mixture of cis-[Pd(C6F5)2L2] and [NBu4]2[Pt(C6F5)4], while its reaction with CO yields a mixture of [NBu4][Pt(C6F5)3(CO)] and [NBu4][Pd(C6F5)3(CO)].

ABSTRACT The reactions of [NBu4]2[cis-Pt(C6F5)2(CCR)2](R = But or SiMe3) with HgX2(X = Cl, Br or I) in a 1:1 molar ratio afforded the simple monomeric bis(η2-alkyne)mercury(II) compounds [NBu4]2[{cis-Pt(C6F5)2(CCR)2}HgX2](R = But or SiMe3; X = Cl, Br or I) in which both alkyne units are co-ordinated η2 side-on to the precursor mercury(II) halides. Similar treatment of [NBu4]2[Pt(CCR)4]·2H2O (R = But or SiMe3) with HgX2 in a 1:2 molar ratio gave the corresponding trinuclear 1:2 adducts. All the complexes have been characterized by analytical and spectroscopic data and, in addition, the molecular structure of [NBu4]2[{cis-Pt(C6F5)2(CCSiMe3)2}HgBr2]·CH2Cl2 has been determined by X-ray diffraction methods. The structure of the anion shows that the HgBr2 unit is attached to the dianionic fragment [Pt(C6F5)2(CCSiMe3)2]2– only through η2 side-on co-ordination of the two (trimethylsilyl)ethynyl ligands. The platinum–mercury distance is 3.627(1.5)Å.

ABSTRACT The binuclear double-bridged acetylide complexes [Pt(μ-CCR)(C6F5)PPh3)]2 [R = Ph (1), But (2), SiMe3 (3)] have been synthesized from [trans-Pt(CCR)2(PPh3)2] and [cis-Pt(C6F5)2(THF)2] (THF = tetrahydrofuran). The crystal structure of [Pt(μ-CCPh) (C6F5)(PPh3)]2 (1) has been established by X-ray diffraction methods. The structure shows that two identical [(PPh3)(C6F5)PtCCPh] units are joined together through η2-bonding of MCCPh units. This indicates that the complex is formed via a rearrangement of groups between the two metal centres. Treatment of [Pt(μ-CCR)(C6F5)(PPh3)]2 with L (L = PPh3, py = pyridine) produces simple bridge-cleavage reactions giving the mono-nuclear complexes [trans-Pt(C6F5)(CCR)(PPh3)L] (4–9).

ABSTRACT The reaction of the NBu+4 salt of trans-[PtCl2(C6Cl5)2]2− with AgNo in acetone-methanol affords polymeric [Pt(C6Cl5)2(μ-Cl)2Ag]x−x, as the NBu+4 salt. The chain anion consists of planar Pt(C6Cl5)2Cl2 units linked by Ag atoms, in which there are AgCl bonds of two types: those which result in Pt(μ-Cl)Ag links and those in which ortho-Cl atoms of C6Cl5 units make close approaches (3.01 and 3.09 Å) to Ag atoms.

... A Compound Displaying an Arene-Platinum Interaction Jose M. Casas, Juan Fornies,* Antonio Martin, and Babil Menjbn ... Faller, JW; Smart, C. J. Organometallics 1989,8,602. Green, M. LH;Joyner, D. D.; Wallis, M. J. Chem. Soc., Dalton Trans. 1987,2823. ...

... Chem.1996, 35, 6599. (e) Casas, JS; Castiñeiras, A.; Haiduc, I.; Sanchez, A.; Sordo, J.; Vasques-Lopez, EM Polyhedron1994, 13, 805. (f) Atencio, R.; Barberá, J.; Cativiela, C.; Lahoz, FJ; Serrano, JL; Zurbano, MM J. Am. Chem. Soc.1994, 116, 11558. ...

ABSTRACT The highly reactive acetone imine can be synthesized, from acetone and ammonia, and stabilized in situ by coordination to a silver atom in a very selective process which involves the presence of an (azaindolato)(pentafluorophenyl)platinum(II) complex. The stability of the dinuclear complex allows full characterization of the acetone imine molecule and provides a route to stabilize new, reactive imines.

Reaction of different "Cd(N-N)(2)(2+)" (N-N = bpy, dmbpy, phen) or "Cd(trpy)(2+)" fragments with cis- or trans- (5) dianionic bis(alkynyl)platinate substrates [Pt(C(6)F(5))(2)(C[triple bond]CR)(2)](2-) (R = Ph a, Tol b) leads to the generation of novel bimetallic neutral Platinum-Cadmium derivatives, which show photoluminescence (PL) strongly influenced by the structure and the media. In complexes [cis-Pt(C(6)F(5))(2)(C[triple bond]CR)(2)Cd(N-N)(2)] (N-N = bpy (1), dmbpy (2), phen (3)), the dianionic cis-bis(alkynyl)platinate fragment interacts with the "Cd(N-N)(2)(+2)" unit mainly through both the C(alpha) atoms (d(Cd-C(alpha)) = 2.417(5)-2.554(5) A) and the Pt center (d(Pt-Cd) approximately 3.10 A); while in complexes [cis-Pt(C(6)F(5))(2)(C[triple bond]CR)(2)Cd(trpy)] (4), probably because of the presence of only three Cd-N bonds, the Pt-Cd interaction is enhanced (d(Pt-Cd) approximately 3.00 A), the Cd(II) atom being additionally solvated with acetone or H(2)O. By contrast, in complexes [trans-Pt(C(6)F(5))(2)(C[triple bond]CR)(2)Cd(bpy)(2)] (6) the Cd center is found to be in a distorted trigonal-bipyramid coordination, interacting with one of the Pt-C(alpha) bonds of the platina-bis(alkynyl) unit with very short Cd-C(alpha) (2.376(10) A) and Pt-Cd (2.8931(6) A) bond distances. Bimetallic complexes 1-4, having cis-configured platinum fragments, exhibit, in solid state, blue and/or green phosphorescence with contribution of close emissive states of different natures: metal (Pt, Cd) perturbed pi pi* intraligand (alkynyl, polyimine) manifolds mixed, to a greater (trpy complexes 4) or lesser extent, with (Pt-Cd) charge transfer…

The bidentate N-donor ligands 2-aminopyridine (2-ampy), 7-azaindolate (aza) and 1,8-naphthyridine (napy) have been used to study the steric effect of pentafluorophenyl groups in the synthesis of binuclear platinum(II) complexes. The 2-ampy and aza ligands bridge two "Pt(C 6F 5) 2" fragments with Pt...Pt distances of 4.1 and 3.4 A, respectively (complexes 1 and 3). Under the same reaction conditions the napy ligand shows chelating behavior and makes the mononuclear complex ( A) highly reactive because of its strained coordination. One of the Pt-N bonds of the chelating complex is broken on reaction with HX {X = Cl ( 4), Br ( 5)} because of protonation while the anion X (-) occupies a created vacant site. The resulting mononuclear complex eliminates C 6F 5H when refluxed, and a binuclear complex ( 6) with two napy ligands bridging two "Pt(C 6F 5)Cl" fragments is obtained. The reaction of A with HPPh 2 affords a mononuclear complex ( 7) analogous to complexes 5 and 6, but reflux gives a binuclear complex ( 8) with the two napy ligands terminally bound and the PPh 2 groups bridging the "Pt(C 6F 5)napy" moieties. The reaction of A with HCCPh gives a binuclear complex; moreover, the final product does not depend on the ratio of complex A to HCCPh. Complexes 1, 4, 6, 9 have been structurally characterized by X-ray diffraction.

... Molecular Structure of (C6F&(SC4H8)PtAgPPh3 F. A. Cotton,* LR Falvello, R. Uson,* J. Fornies, M. Tomas, J. M. Casas, and I. Ara ... The molecular structure of a representative compound (L = SC4H,; L' = PPh,) has been determined by a single-crystal X-ray diffraction study. ...

Six pentafluorophenylplatinum(II) complexes containing proton acceptor atoms (F) and pyridine-like aromatic ligands able to act as proton donors have been synthesized and characterized, with emphasis on the factors that mediate their supramolecular aggregation in the solid state--hydrogen bonds and pi-pi interactions. The crystal structure analyses of the mononuclear complexes cis-[Pt(C6F5)2(napy)](1), cis-[Pt(C6F5)2(CH2napy)](3), cis-[Pt(C6F5)2(2-ammpy)](5), and cis-[Pt(C6F5)2(2-bipym)](6) reveal the influence of D-HPt and D-HF (D=C, N) hydrogen bonding on the organization of molecules into stacks, which can be further interconnected to generate channels. The prevalence of hydrogen bonding over pi-pi interactions between aromatic rings in establishing the nature of the observed supramolecular aggregation is demonstrated.

A novel series of [PtTl(2)(C[triple chemical bond]CR)(4)](n) (n = 2, R = 4-CH(3)C(6)H(4) (Tol) 1, 1-naphthyl (Np) 2; n = infinity, R = 4-CF(3)C(6)H(4) (Tol(F)) 3) complexes has been synthesized by neutralization reactions between the previously reported [Pt(C[triple chemical bond]CR)(4)](2-) (R = Tol, Tol(F)) or novel (NBu(4))(2)[Pt(C[triple chemical bond]CNp)(4)] platinum precursors and Tl(I) (TlNO(3) or TlPF(6)). The crystal structures of [Pt(2)Tl(4)(C[triple chemical bond]CTol)(8)]4 acetone, 14 acetone, [Pt(2)Tl(4)(C[triple chemical bond]CNp)(8)]3 acetone1/3 H(2)O, 23 acetone 1/3 H(2)O and [[PtTl(2)(C[triple chemical bond]CTol(F))(4)](acetone)S](infinity) (S = acetone 3 a; dioxane 3 b) have been solved by X-ray diffraction studies. Interestingly, whereas in the tolyl (1) and naphthyl (2) derivatives, the thallium centers exhibit a bonding preference for the electron-rich alkyne entities to yield crystal lattices based on sandwich hexanuclear [Pt(2)Tl(4)(C[triple chemical bond]CR)(8)] clusters (with additional Tlacetone (1) or Tlnaphthyl (2) secondary interactions), in the C(6)H(4)CF(3) (Tol(F)) derivatives 3 a and 3 b the basic Pt(II) center forms two unsupported Pt-Tl bonds. As a consequence 3 a and 3 b form an extended columnar structure based on trimetallic slipped PtTl(2)(C[triple chemical bond]CTol(F))(4) units that are connected through secondary Tl(eta(2)-acetylenic) interactions. The luminescent properties of these complexes, which in solution (blue; CH(2)Cl(2) 1,2; acetone 3) are very different to those in solid state (orange), have been studied. Curiously, solid-state emission from 1 is dependent on the presence of acetone (green) and its crystallinity. On the other hand, while a powder sample of 3 is pale yellow and displays blue (457 nm) and orange (611 nm) emissions, the corresponding pellets (KBr, solid) of 3, or the fine powder obtained by grinding, are orange and only exhibit a very intense orange emission (590 nm).

Ein Sechskernkomplex mit ungewöhnlicher Struktur ist das Anion 1, X = Cl: Die R2Pt(μ‐Cl)2PtR2‐Gruppen (R = C6Cl5) sind mit den beiden Ag‐Atomen durch Pt→Ag‐Donorbindungen verknüpft. Cl‐Atome der C6Cl5‐Liganden und möglicherweise der μ‐Cl‐Brücken übertragen ebenfalls Elektronendichte auf die Ag‐Atome. 1, X = Br, wurde ebenfalls synthetisiert. magnified image

... By Rafael Us&, Juan Forniks, Milagros Tomas, and Josk M. Casas The electron-rich metal centers in mono-and binuclear platinum(n) complexes containing perhalophenyl ligands are able to donate electron ... [6] PtMe,(bpy) shows a similar behavior; G. J. Arsenault, CM Anderson ...

ABSTRACT The course of the reactions of Q2[cis-Pt(C6F5)2(CCR)2] (Q = PPh3Me, R = Ph 1a; Q = NBu4, R = tBu 1b, SiMe3 1c) with [M(μ-Cl)(COD)]2 (M = Rh, Ir) is strongly influenced by the metal and the substituents, as well as the stoichiometry. Thus, whereas treatment of 1a with either 0.5 or 1 equiv of [Rh(μ-Cl)(COD)]2 gives the chelating-type binuclear highly polar compound (PPh3Me)[cis-Pt(C6F5)2(μ-1κCα:η2-CCPh)2Rh(COD)], 2a, analogous reactions using 1b as the precursor afford only the trinuclear complex (NBu4)[{cis-Pt(C6F5)2(μ-1κCα:η2-CCtBu)2}{Rh2(μ-Cl)(COD)2}], 4b. On the other hand, related bi- and trinuclear SiMe3 derivatives (NBu4)[cis-Pt(C6F5)2(μ-1κCα:η2-CCSiMe3)2Rh(COD)], 2c, and (NBu4)[{cis-Pt(C6F5)2(μ-1κCα:η2-CCSiMe3)2}{Rh2(μ-Cl)(COD)2}], 4c, are easily obtained by treating 1c with the binuclear rhodium substrate in the adequate molar ratio [1:0.5 for 2c; 1:1 for 4c]. Complex 2b and, alternatively, 2a,c derivatives can be produced by reacting 1 with the cationic solvento species [Rh(COD)(Et2O)x]+ (prepared in situ). The molecular structures of 2a and 4b have been confirmed by X-ray diffraction. By contrast, whereas the reactions of 1a,b with [Ir(μ-Cl)(COD)]2 lead to the formation of undefined products, the heterobinuclear σ,π double-alkynyl-bridged complex (NBu4)[cis-Pt(C6F5)2(μ-1κCα:η2-CCSiMe3)(μ-η2:2κCα-CCSiMe3)Ir(COD)], 3c, (X-ray) is isolated from reaction of 1c with the dimer iridium complex regardless of the molar ratio used (1:0.5 or 1:1).