ADVERTISEMENT RETURN TO ISSUEPREVNoteNEXTSynthesis and Crystal Structure of the First Cluster Displaying PdI−AgI Interactions: [Ag2Pd2(SC6F5)2(SO3CF3)(dppm)3]SO3CF3·CH2Cl2Rafael Usón, Miguel A. Usón, and Santiago HerreroView Author Information Departamento de Química Inorgánica, Instituto de Ciencia de Materiales de Aragón, Universidad de Zaragoza-CSIC, E-50009 Zaragoza, Spain Cite this: Inorg. Chem. 1997, 36, 25, 5959–5961Publication Date (Web):December 3, 1997Publication History Received24 April 1997Published online3 December 1997Published inissue 1 December 1997https://pubs.acs.org/doi/10.1021/ic970457ihttps://doi.org/10.1021/ic970457ibrief-reportACS PublicationsCopyright © 1997 American Chemical SocietyRequest reuse permissionsArticle Views131Altmetric-Citations14LEARN ABOUT THESE METRICSArticle Views are the COUNTER-compliant sum of full text article downloads since November 2008 (both PDF and HTML) across all institutions and individuals. These metrics are regularly updated to reflect usage leading up to the last few days.Citations are the number of other articles citing this article, calculated by Crossref and updated daily. Find more information about Crossref citation counts.The Altmetric Attention Score is a quantitative measure of the attention that a research article has received online. Clicking on the donut icon will load a page at altmetric.com with additional details about the score and the social media presence for the given article. Find more information on the Altmetric Attention Score and how the score is calculated. Share Add toView InAdd Full Text with ReferenceAdd Description ExportRISCitationCitation and abstractCitation and referencesMore Options Share onFacebookTwitterWechatLinked InRedditEmail Other access optionsGet e-AlertscloseSupporting Info (2)»Supporting Information Supporting Information SUBJECTS:Ligands,Metals,Oxygen,Palladium,Silver Get e-Alerts

Reactions of the anionic platinum complexes (NBu(4))[Pt(PPh(3))(C(6)F(5))(2)(OCOCH(3))] (1) and (NBu(4))(2)[Pt(C(6)F(5))(3)(S)] (S = methanol or acetone) with Tl(I) salts afford the heterometallic neutral cis-[(C(6)F(5))(2)(PPh(3))Pt(&mgr;(2)-OOCCH(3))Tl] (2) and the dimeric dianionic (NBu(4))(2)[{(C(6)F(5))(3)Pt}(2){(&mgr;(2)-O,&mgr;(3)-O'CCH(3))Tl}(2)] (3). Both complexes display Pt-Tl bonds with bond lengths of 2.994(1) Å and 2.884(1) Å, respectively, the latter being the shortest Pt-Tl(I) distance reported so far. The structure of both compounds has been established by X-ray studies.

ADVERTISEMENT RETURN TO ISSUEPREVArticleNEXTSynthesis and Structure of (NBu4)2[Tl{Pt(C6F5)4}2], the First Paramagnetic Compound Containing Thallium(II)Rafael Uson, Juan Fornies, Milagros Tomas, Raquel Garde, and Pablo J. AlonsoCite this: J. Am. Chem. Soc. 1995, 117, 6, 1837–1838Publication Date (Print):February 1, 1995Publication History Published online1 May 2002Published inissue 1 February 1995https://pubs.acs.org/doi/10.1021/ja00111a025https://doi.org/10.1021/ja00111a025research-articleACS PublicationsRequest reuse permissionsArticle Views135Altmetric-Citations50LEARN ABOUT THESE METRICSArticle Views are the COUNTER-compliant sum of full text article downloads since November 2008 (both PDF and HTML) across all institutions and individuals. These metrics are regularly updated to reflect usage leading up to the last few days.Citations are the number of other articles citing this article, calculated by Crossref and updated daily. Find more information about Crossref citation counts.The Altmetric Attention Score is a quantitative measure of the attention that a research article has received online. Clicking on the donut icon will load a page at altmetric.com with additional details about the score and the social media presence for the given article. Find more information on the Altmetric Attention Score and how the score is calculated. Share Add toView InAdd Full Text with ReferenceAdd Description ExportRISCitationCitation and abstractCitation and referencesMore Options Share onFacebookTwitterWechatLinked InRedditEmail Other access optionsGet e-AlertscloseSupporting Info (2)»Supporting Information Supporting Information Get e-Alerts

Novel anionic xanthate complexes of platinum(II) with the xanthate ligands displaying different cordiantion modes have been prepared: (a) mononuclear (NBu4)[Pt(C6X5)2(S2COEt)] (X = F (1) or Cl (2)), where the xanthate ligand acts as a che;ate; (b) mononuclear complexes (NBu4)[Pt(6X5)2(SC(S)OEt)PPh3] (X = F (3) or Cl (4)) contaning monodentate SC(S)OEt ligands; and (c) tetranuclear complexes (NBu4)2{Pt46X5)8([μ3-S)SCOEt]}2 (X [= F (5) or Cl (6)), where one of the S atoms bridges three platinumm centres, an unprecedented bonding mode for the xanthate ligand. The structures of complexes 1 and 5 have been established by single crystal X-ray diffraction. Compound 1 is triclinic, space group P1, with a = 9.4 72(1)b = 11.005(2), c = 18.561(2) Å, α = 75.90(1), β = 81.23(1), ψ = 75.99(1)°, V = 1811.7(4) Å3 and Z = 2. The structure was refined tor residuals of R = 0.0299 and fRw = 0.0419. Complex 5 is also triclinic, space group P1, with a = 11.121(1), b = 15.184(1), c = 16.722(1) Å, α = 64.17(1), β = 80.56(1), ψ = 88.41(1) Å3 and Z = 1. The structure was refined to residuals of R = 0.0409 and Rw = 0.0417.

Binuclear M2 (MPt, Pd) complexes with bridging NN (NNbpy) [NBu4]2[M2(μ-NN)(C6F5)6], mononuclear Pt complexes with monodentate bpy or phen [NBu4][Pt(C6F5)3(NN)] or neutral mononuclear Pt complexes with chelating phen [Pt(C6F5)2(NN)] or Pd complexes with bpy or phen [Pd(C6F5)2(NN)] can be prepared starting from [NBu4]2[M2(μ-C6F5)2(C6F5)4] by adequate choice of solvents and reactions conditions. The crystal structures of [PPN]2[Pt2(μ-bpy)(C6F5)6] and [NBu4][Pt(C6F5)3(phen)] have been established by X-ray crystallography.

Reacting (NBu4)[trans-PtX2(C6Cl5)L] (X = Cl, L = PPh3, SC4H8, p-MeC6H4NH2, NC5H5; X = Br, L = PPh3) with AgClO4 in 1:1 molar ratio leads to the polymeric complexes [PtAgX2(C6Cl5)L]x (X = Cl, L = PPh3 (1), SC4H8 (2), p-MeC6H4NH2 (3), NC5H5 (4); X = Br, L = PPh3 (5)). The structure of complex 1 has been solved by single-crystal X-ray diffraction. The compound crystallizes in the orthorhombic system, space group Pna2(1) with a = 10.327(3) angstrom, b = 18.094(6) angstrom, c = 18.451(5) angstrom, V = 3447.69 angstrom3, and Z = 4. The structure was refined to residuals of R = 0.0414 and R(w) = 0.0492. Each repeat unit is formed by the interaction of the square planar fragment [trans-PtCl2(C6Cl5)PPh3]- with Ag+ via a Pt-Ag bond (Pt-Ag = 2.855(2) angstrom) which is supported by a Pt(mu-Cl(2))Ag bridge. These units are connected by a Pt(mu-Cl(1))Ag bridging system, resulting in the formation of the polymer. The silver atom also makes a short contact with one o-Cl atom of the C6Cl5 group (o-Cl...Ag = 2.838(6) angstrom). Complex 1 reacts with PPh3 (1:1) to give [PPh3(C6Cl5)ClPt(mu-Cl)AgPPh3], but the reaction with SC4H8 results in the elimination of AgCl and formation of [PtCl(C6Cl5)PPh3(SC4H8)].

A previously reported compound [NBu(4)] [Pt-2(mu-C6F5Cl)(mu-C6F5)(C6F5)(4)] (A) reacts with OH- or OR(-) (R = Me, Et) to give the dinuclear Pt(III) complexes [NBu(4)](2)[Pt-2(mu-C6F4O)(2)(C6F5)(4)] (1) or [NBu(4)](2)[Pt-2{mu-C6F4(OR)(2)}(2)-(C6F5)(4)] with R = Me (2) or Et (3). These three products contain pairs of quinone (C6F4O) or quinon-like (C6F4(OR)(2)) bridges and 1 and 2 have Pt-Pt single bonds with lengths of 2.570(1) and 2.584(1) Angstrom, respectively. The anions are strictly centrosymmetric and the central C2Pt(mu-C)(2)PtC2 cores have effective mmm symmetry. The mu-C6F4(OR)(2) ligands are readily hydrolyzed to give mu-C5F4O ligands. The crystallographic data are as follows. For 1,, a = 12.055(2) Angstrom, b = 12.915(2) Angstrom, c = 13.055(2) Angstrom, alpha = 98.12(1)degrees, beta = 114.30(1)degrees, gamma = 86.02(1)degrees, V = 1833.7(5) Angstrom(3), Z = 1. For 2, P2(1)/c, a = 12.220(1) Angstrom, b = 21.552(2) Angstrom, c = 16.272(2) Angstrom, beta = 96.66(1)degrees, V = 4256(1) Angstrom(3), Z = 2.

The complexes cis-[M(C6F5)2(thf)2] (M = Pd or Pt, thf = tetrahydrofuran) react (2:1) with [NMe4]2[M'(SC6F5)4][M'= Pd or Pt] or Q2[M'2(SC6F5)6] [M' = Pd, Q = NBu4; M' = Pt, Q = NMe4 or P(CH2Ph)Ph3] to give homo- or hetero-metallic tri- or, respectively, tetra-nuclear dianions. The structure of the tetranuclear complex [P(CH2Ph)Ph3]2[(C6F5)2Pd(mu-SC6F5)2Pt(mu-SC6F5)2Pt(mu-SC6F5)2Pd(C6F5)2] has been established by single-crystal X-ray crystallography: the dianion possesses a crystallographic inversion centre; space group P1BAR, a = 12.247(2), b = 12.901(2), c = 17.942(3) angstrom, alpha = 84.47(2), beta = 78.20(2), gamma = 77.21(2)degrees, Z = 1, and R = 0.0454. The co-ordination at the metal atoms is planar. The outer (palladium) planes form an angle of 28.20(11)-degrees with the inner ones.

The previously reported trinuclear, (C6F5)-bridged compound (NBu4)[Pt2(mu-C6F5)2(mu-AgOEt2)(C6F5)4], 1, reacts with an excess of molecular chlorine in toluene/CCl4 to give the novel metal-metal bonded, garnet-colored complex 3, (NBu4)[(C6F5)2Pt(mu-C6F5Cl)(mu-C6F5)Pt(C6F5)2]. Compound 3 is the result of addition of one chlorine atom to a bridging C6F5 ligand, with concomitant oxidation of the dinuclear core to a singly bonded Pt(III)-Pt(III) unit with planar D2h geometry. Compound 1 also reacts with an excess of Br2 or 12 in toluene to give the black, dinuclear Pt(II)-Pt(III)compound(NBu4)[(C6F5)2Pt(mu-C6F5)2Pt(C6F5)2],4, which also has a planar core, The garnet complex 3 can also be prepared by the reaction of the dinuclear, (C6F5)-bridged complex (NBu4)2[Pt2(mu-C6F5)2(C6F5)4],2, with Cl2 in CCl4, and by the reaction of compound 4 with Cl2 in CH2Cl2/CCl4. An SCF-Xalpha-SW study of compound 4 shows that the HOMO, 15b1u, which contains an unpaired electron, takes its major contribution from the pi system of the bridging (C6F5) ligands, thus explaining the vulnerability of the bridging ligand to chemical attack. Complex 3 has been characterized by F-19 NMR spectroscopy and by X-ray diffraction. Complex 4 was studied by EPR spectroscopy and X-ray diffraction. Compound 3, Pt2C52H36NF30Cl, crystallizes in the monoclinic crystal system, space group C2/c, with a = 12.101(3) angstrom, b = 21.047(6) angstrom, c = 21.977(8) angstrom, beta = 95.57(3)degrees, V = 5571(3) angstrom3 at -83-degrees-C, and Z = 4. A model of 353 parameters was refined to residuals of R = 0.0629, R, = 0.0909, and quality of fit = 1.708. Compound 4, Pt2C52H36NF30, is monoclinic, space group C2/c, with a = 12.198(6) angstrom, b = 20.592(6) angstrom, c = 22.223(7) angstrom, beta = 95.23(3)degrees, V = 5559(6) angstrom3 at 21-degrees-C, and Z = 4. The structure was refined to residuals of R = 0.043 1, R(w) = 0.0498, and quality of fit = 0.998. The Pt-Pt distances are 2.573(2) and 2.611(2) angstrom in 3 and 4, respectively. Cyclic voltammetry shows that a reversible one-electron process interconverts complexes 2 and 4; however, oxidation of complex 4 by a process presumed to involve ligand reactivity is irreversible.

A Pd(I) cluster of high nuclearity can be synthesized by adequate choice of a palladium(II) complex containing two different bridge-forming ligands and reacting it with a palladium(0) complex.

ADVERTISEMENT RETURN TO ISSUEPREVArticleNEXTSynthesis and structure of tetrabutylammonium hexakis(perfluorophenyl)bis(.mu.-tetrahydrothiophene)diplatinum argentate(1-), a trinuclear compound displaying two structurally different anions in the solid stateR. Uson, J. Fornies, L. R. Falvello, M. Tomas, J. M. Casas, and A. MartinCite this: Inorg. Chem. 1993, 32, 23, 5212–5215Publication Date (Print):November 1, 1993Publication History Published online1 May 2002Published inissue 1 November 1993https://doi.org/10.1021/ic00075a045RIGHTS & PERMISSIONSArticle Views50Altmetric-Citations19LEARN ABOUT THESE METRICSArticle Views are the COUNTER-compliant sum of full text article downloads since November 2008 (both PDF and HTML) across all institutions and individuals. These metrics are regularly updated to reflect usage leading up to the last few days.Citations are the number of other articles citing this article, calculated by Crossref and updated daily. Find more information about Crossref citation counts.The Altmetric Attention Score is a quantitative measure of the attention that a research article has received online. Clicking on the donut icon will load a page at altmetric.com with additional details about the score and the social media presence for the given article. Find more information on the Altmetric Attention Score and how the score is calculated. Share Add toView InAdd Full Text with ReferenceAdd Description ExportRISCitationCitation and abstractCitation and referencesMore Options Share onFacebookTwitterWechatLinked InReddit PDF (545 KB) Get e-AlertsSupporting Info (1)»Supporting Information Supporting Information Get e-Alerts

The result of the reaction between [NBu4][Pt(C6F5)3(tht)] (tht = SC4H8, tetrahydrothiophene) and AgClO4 in CH2Cl2 is a trinuclear anionic complex which has been isolated in the form of its tetrabutylammonium salt [NBu4][Pt2-Ag(mu-tht)2(C6F5)6] (1). Pt2AgC60F30H52NS2 is triclinic, space group P1, with a = 13.486(3) angstrom, b = 14.697(4) angstrom, c = 17.333(4) angstrom, alpha = 106.01(2)degrees, beta = 90.50(2)degrees, gamma = 98.03(3)degrees, V = 3262.4(13) angstrom, and Z = 2. As a unique proof of the concerted nature of the electronic effects operating at the aceptor silver center, the asymmetric unit contains two independent half-anions (lying on centers of inversion) with different bond distances in their cores: anion 1a, Pt-Ag = 2.783(1) angstrom and Ag-S = 2.778(2) angstrom; anion 1b, Pt-Ag = 2.862(1) angstrom and Ag-S = 2.547(2) angstrom. H-1 and F-19 NMR spectra point to dynamic behavior in solution of the complex anion.

Complexes of the general formula cis-[M(SC6F5)2L2] (M  Ni, Pd, or Pt; L2  dppm [bis(diphenylphosphino)methane], dppe [ 1,2-bis(diphenylphosphino)ethane], or 2PPh3 were synthesized by the reaction (1 : 2 between the corresponding cis-[MCl2L2] and Tl(SC6F5). When treated with cis-[M(C6F5)2(THF)2] (M  Pd or Pt; THF  OC4H8 they yield geminal homo- or hetero-binuclear compounds, which were characterized by IR, NMR and mass spectroscopy.

Two unprecedented reactions between (NBu4)2[Pt(C6F5)4] or (NBu4)2[Pt(μ-Cl)(C6F5)2]2 and Hg(NO3)2 lead to trinuclear (NBu4)2[(C6F5)3(μ-OH)(μ-HgC6F5)Pt(C6F5)3] (1) or hexanuclear (NBu4)2[(μ-OH)2{(C6F5)2Pt(μ-OH)(μ-HgCl)Pt(C6F5)2}2] (2), respectively. The structures of both complexes have been established by X-ray studies and contain OH bridges between each pair of platinum atoms and donor-acceptor Pt→Hg bonds unsupported by any covalent bridges. The crystallographic parameters are as follows: 1: monoclinic, C2/c with a=19.787(6), b=21.495(6), c=18.242(5) Å, β=96.18(3)°, Dcalc=1.948 g cm−3 for Z=4 formula units and R=0.037 utilizing 3090 data with Fo2 ⩾ 3σ(Fo2); 2: triclinic, P1 with a=14.23(1), b=17.81(2), c=20.55(2) Å, α=87.03(7), β=83.92(7), γ=83.46(5)°, Dcalc=2.129 g cm−3 for Z=2 and R=0.079 using 6507 reflections with Fo2 ⩾(2.5σ Fo2).

The complexes cis-[pt(C6F5)2(RC=CR)2] (R = Et 1a or Ph 1b) have been prepared by treating cis-[Pt(C6F5)2(thf)2] (thf = tetrahydrofuran) with the appropriate alkyne. They undergo facile ligand exchange with either cis-[Pt(C6F5)2(thf)2] or [NBun4]2[Pt(C6F5)4] giving rise respectively to neutral cis-[Pt(C6F5)2(thf) (RC=CR)] 2 or anionic [NBun4][Pt(C6F5)3(PhC-CPh)] 7b mono(eta2-alkyne) derivatives. A series of mono(eta2-alkyne) complexes of formulae cis-[Pt(C6F5)2L(RC=CR)] (L = pyridine 3a, 3b; PPh3 4a; SbPh3 5b; or CO 6a, 6b) and [N(PPh3) 2][Pt(C6F5)3(EtC=CEt)] 7a has also been prepared. None of these complexes except 7b shows nu(C=C) absorptions in their IR spectra. The molecular structures of complexes lb and 7b have been established by X-ray diffraction studies: 1b, monoclinic, space group C2/c, a = 19.177(4), b = 8.4971(4), c = 19.790(3) angstrom, beta = 103.297(14)degrees and Z = 4 (C2 symmetry imposed); 7b, monoclinic, space group P2(1)/c, a = 10.5179(9), b = 17.5834(20), c = 25.369(5) angstrom, beta = 99.376(11)degrees and Z = 4. Parameters within the acetylene moiety of 1b suggest that the platinum-->alkyne pi-back bonding is minimal.

Donor-acceptor Pt→Ag bonds formed by reactions between anionic platinum complexes and silver salts or complexes are the subject of this review. We discuss their structural features and the role played by the charge of the anions and by o-X…Ag interactions in the stability and spatial arrangement of the resulting heteronuclear complexes. The extension of these studies to other M→M′ systems is briefly commented.

The trinuclear compound (NBu4)2{Pb[Pt(C6F5)4)2} which has been prepared in 82% yield, displays a linear Pt-Pb-Pt moiety. Eight Pb...o-F short contacts and a stereochemically inactive lone pair on the lead atom are other striking features in the anion of this unprecedented complex. The Pb-Pt distances arc 2.769 (2) and 2.793 (2) angstrom, the average Pb...o-F contact is 2.845 angstrom, and the Pt-Pb-Pt angle is 178.6 (1)-degrees.