- THE PHOTODECOMPOSITION OF PLATINACYCLOALKANES IN SOLUTION II. 1,4-BUTANEDIYLPLATINUM(II) AND (IV) COMPOUNDS
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The products of the photolysis of a number of platinacyclopentanes is solution at 25 deg C under a variety of conditions have been determined.With (L = PMe2Ph, PPh3) in CH2Cl2, CH2Br2 and (CH3)2SO the hydrocarbon products are exclusively ethylene and but-1-ene.Formation of the latter through a 1,3-hydrogen shift is preceded by phosphine ligand dissociation.The photolysis of gave methane, ethylene, but-1-ene and n-pentane together with a little n-butane, the methane being formed from internal hydrogen abstraction by the CH3 group in the excited reactant molecule.Photodecomposition of the platinum(II) compounds (L = (PMe2Ph)2, (PPh3)2, Ph2PCH2CH2PPh2) gave ethylene, but-1-ene, pent-1-ene (with the halogenated solvents) and with some systems appreciable yields of n-butane, the latter being the result of internal abstraction of two hydrogen atoms by the C4H8 moiety.The formation of pentene is probably preceeded by the addition of CH2Cl2 or CH2Br2 to the excited reactant molecule.Addition of diphenylphosphine promotes the production of n-butane.
- Perkins, Duncan C.L.,Puddephatt, Richard J.,Tipper, Charles F.H.
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- Reversible capture of small molecules on bimetallaborane clusters: Synthesis, structural characterization, and photophysical aspects
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Metallaborane compounds containing two adjacent metal atoms, [(PMe 2Ph)4MM′B10H10] (where MM′ = Pt2, 1; PtPd, 7; Pd2, 8), have been synthesized, and their propensity to sequester O2, CO, and SO 2 and to then release them under pulsed and continuous irradiation are described. Only [(PMe2Ph)4Pt2B 10H10], 1, undergoes reversible binding of O2 to form [(PMe2Ph)4(O2)Pt2B 10H10] 3, but solutions of 1, 7, and 8 all quantitatively take up CO across their metal-metal vectors to form [(PMe2Ph) 4(CO)Pt2B10H10] 4, [(PMe 2Ph)4(CO)PtPdB10H10] 10, and [(PMe2Ph)4(CO)Pd2B10H10] 11, respectively. Crystallographically determined interatomic M-M distances and infrared CO stretching frequencies show that the CO molecule is bound progressively more weakly in the sequence {PtPt} > {PtPd} > {PdPd}. Similarly, SO2 forms [(PMe2Ph)4(SO 2)Pt2B10H10] 5, [(PMe 2Ph)4(SO2)PtPdB10H10] 12, and [(PMe2Ph)4(SO2)Pd2B 10H10] 13 with progressively weaker binding of the SO 2 molecule. The uptake and release of gas molecules are accompanied by changes in their absorption spectra. Nanosecond transient absorption spectroscopy clearly shows that the O2 and CO molecules are liberated from the bimetallic binding site with high quantum yields of about 0.6. For 3, in addition to dioxygen release in the triplet ground state, singlet oxygen O2(1Δg) was also detected with a quantum yield 2 and CO molecules, from 3 and 4 respectively, is an ultrafast process taking place on a time scale of tens of picoseconds. For SO2, the release is even faster (2 and Pd 2 adducts, 5 and 13, the release of SO2 is significantly slower (>1 ns). All these compounds may have potential to serve as light-triggered local and instantaneous sources of the studied gases.
- Bould, Jonathan,Base, Tomas,Londesborough, Michael G. S.,Oro, Luis A.,MacIas, Ramon,Kennedy, John D.,Kubat, Pavel,Fuciman, Marcel,Polivka, Tomas,Lang, Kamil
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p. 7511 - 7523
(2011/10/03)
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- The molecular structure of a 2-aryl-1,3,2-dioxaphospholane and its coordination behaviour towards platinum(II) species; molecular structures of four platinum(II) complexes
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The molecular structure of the 2-aryl-1,3,2-dioxaphospholane, 2,6-(CF3)2-C6H3-P(OCH2)2 (1), has been determined by single-crystal X-ray diffraction at 120 K. Its reactions with the platinum
- Dillon, Keith B.,Goeta, Andrés E.,Monks, Philippa K.,Shepherd, Helena J.
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p. 606 - 612
(2010/06/12)
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- Synthesis and characterisation of triselenocarbonate [CSe3] 2- complexes
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[Pt(CSe3)(PR3)2] (PR3 = PMe3, PMe2Ph, PPh3, P(p-tol)3, 1/2 dppp, 1/2 dppf) were all obtained by the reaction of the appropriate metal halide containing complex with carbon diselenide in liquid ammonia. Similar reaction with [Pt(Cl)2(dppe)] gave a mixture of triselenocarbonate and perselenocarbonate complexes. [{Pt(μ-CSe3)(PEt 3)}4] was formed when the analogous procedure was carried out using [Pt(Cl)2(PEt3)2]. Further reaction of [Pt(CSe3)(PMe2Ph)2] with [M(CO)6 (M = Cr, W, Mo) yielded bimetallic species of the type [Pt(PMe2Ph) 2(CSe3)M(CO)5] (M = Cr, W, Mo). The dimeric triselenocarbonate complexes [M{(CSe3)(η5-C 5Me5)}2] (M = Rh, Ir) and [{M(CSe 3)(η6-p-MeC6H4 iPr)}2] (M = Ru, Os) have been synthesised from the appropriate transition metal dimer starting material. The triselenocarbonate ligand is Se,Se' bidentate in the monomeric complexes. In the tetrameric structure the exocyclic selenium atoms link the four platinum centres together. The Soyal Society of Chemistry 2005.
- Burchell, Colin J.,Aucott, Stephen M.,Slawin, Alexandra M. Z.,Woollins, J. Derek
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p. 735 - 739
(2007/10/03)
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- Synthesis and characterisation of cyanodithioimidocarbonate [C2N2S2]2- complexes
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[PPh4]2[M(C2N2 S2)2] (M = Pt, Pd) and [Pt(C2N2S2) (PR3)2] (PR3 = PMe2Ph, PPh3) and [Pt(C2N2S2)(PP)] (PP = dppe, dppm, dppf) were all obtained by the reaction of the appropriate metal halide containing complex with potassium cyanodithioimidocarbonate. The dimeric cyanodithioimidocarbonate complexes [{Pt(C2N2S2) (PR3)}2] (PR3 = PMe2Ph), [M{(C2N2 S2)(η5-C5Me5)}2] (M = Rh, Ir) and [{Ru(C2N2S2) (η6-p-MeC6H41Pr)}2] have been synthesised from the appropriate transition metal dimer starting material. The cyanodithioimidocarbonate ligand is S,S and bidentate in the monomeric complexes with the terminal CN group being approximately coplanar with the CS2 group and trigonal at nitrogen thus reducing the planar symmetry of the ligand. In the dimeric compound one of the sulfur atoms bridges two metal atoms with the core exhibiting a cubane-like geometry.
- Burchell, Colin J.,Aucott, Stephen M.,Milton, Heather L.,Slawin, Alexandra M.Z.,Woollins, J. Derek
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p. 369 - 374
(2007/10/03)
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- Hydroxo and oxo complexes of platinum(II) stabilized by phosphanes: Synthesis and characterization - X-ray structures of cis-[L2Pt(μ- OH)]2(NO3)2 (L = PMe2Ph, PMePh 2) and [{cis-(PMe2<
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The dinuclear hydroxo complexes cis-[L2Pt(μ-OH)] 2(NO3)2 (L = PMe2Ph and PMePh 2) have been characterized by single-crystal X-ray analysis, and their reactivity towards chloride ions has be
- Longato, Bruno,Bandoli, Giuliano,Dolmella, Alessandro
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p. 1092 - 1099
(2007/10/03)
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- The preparation of the first examples of sulfimide complexes of platinum; the X-ray crystal structure of [Pt(Ph2SNH)4]Cl2
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The reactivity of S,S-diphenylsulfimide, Ph2SNH, (1) towards platinum complexes has been investigated. Solutions of 1 and [PtCl2(PMe2Ph)2] show an equilibrium between the starting materials and cis-[PtCl(Ph2SNH)(PMe2Ph)2]Cl; addition of [NH4][BF4] generates pure cis-[PtCl(Ph2SNH)(PMe2Ph)2][BF4] (2). Four equivalents of 1 react with [PPh4]2[PtCl4] over a period of days to give crystalline [Pt(Ph2SNH)4]Cl2 (3); the crystal structure of 3 confirms the expected square planar geometry with significant H-bonding interactions between the cation and the chlorides. (C) 2000 Elsevier Science Ltd.
- Kelly,Macklin,Slawin,Waring
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p. 2077 - 2081
(2008/10/08)
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- Formation of the bidentate [Ph2SNC(Me)N(H)] ligand by metal-assisted sulfimide addition to acetonitrile; X-ray crystal structure of [Pt(Ph2SNH)(Ph2SNC(Me)NH)Cl]Cl.MeCN
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In contrast to similar reactions of Cu, Co and Pd species, the platinum(II) complex [Pt(MeCN)2Cl2] reacts with Ph2SNH (ratio 1:2) in MeCN via a metal assisted addition of the sulfimide to the acetonitrile to give [Pt(Ph2SNH)(Ph2SNC(Me)NH)Cl]Cl.MeCN, the first example of a complex of the bidentate [Ph2SNC(Me)N(H)] ligand.
- Kelly, Paul F.,Slawin, Alexandra M. Z.
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p. 1081 - 1082
(2007/10/03)
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- Preparation and characterization of aryltellurolato-bridged dinuclear complexes of platinum(II)
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Complexes of the type (X=Cl or TeAr; Ar=Ph,4-MeC6H4,4-MeOC6H4,4-EtOC6H4;PR3=PEt3,Pn-Bu3 or PMe2Ph) and (Ar=4-MeC6H4,4-MeOC6H4;P-C=t-Bu2CMe2CH2) have been prepared.These complexes were characterized by elem
- Jain, Vimal K.,Kannan, S.
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p. 349 - 357
(2007/10/02)
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- Amine, Imine, and Aminocarbene Complexes of Platinum(II)
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Solutions of the chloride-bridged binuclear platinum complexes (L=PMe2Ph or PBu3) readily react with the amines NH2Ph, 4-NO2C6H4NH2, 3-MeOC6H4NH2, NHPh2, or NH2Me to produce trans- in the presence or absence of phenylethyne.T
- Cross, Ronald J.,Davidson, Michael F.,Rocamora, Merce
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p. 1147 - 1152
(2007/10/02)
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- Synthesis of heterobimetallic bis(diphenylphosphino)acetylene-bridged palladium-platinum complexes. Crystal and molecular structure of [PdPtCl4(Ph2PC≡CPPh2) 2]·2CHCl3
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Reaction of [(PMe2Ph)PdCl(μ-Cl)2PtCl(PMe2Ph)] (I) with 1,2-bis(diphenylphosphino)acetylene yields the heterobimetallic complex [Cl2Pd(Ph2PC≡CPPh2)2PtCl 2] (II). Solution studies using 31P and 195Pt NMR spectra reveal that II exists in an equilibrium of the type 2[Cl2Pd(Ph2PC≡CPPh2)2PtCl 2] ? [Cl2Pd(Ph2PC≡CPPh2)2PdCl 2] + [Cl2Pt(Ph2PC≡CPPh2)2PtCl 2]. Crystals of II [as the bis(chloroform) solvate] are monoclinic, space group P21/n with two formula units in a cell of dimensions a = 14.415 (3) A?, b = 12.149 (3) A?, c = 15.949 (3) A?, and β= 91.33 (2)°. The bimetallic complex lies about a crystallographic inversion center, and the Pd and Pt atoms are mutually disordered. The structure was solved by the heavy-atom method and refined by full-matrix least-squares calculations with anisotropic thermal parameters; R = 0.033 and Rw = (ΣwΔ2/ΣwF02)1/2 = 0.044 for 2407 observed reflections. The unique metal atom has slightly distorted square-planar geometry with mean M-Cl = 2.344 (2) A and mean M-P = 2.244 (2) A?. The strained 10-membered PtPdP4C4 ring system is nonplanar; there is significant bowing of the P-C≡C-P moiety [mean P-C ≡C = 172.2 (3)°] and enlargement of the M-P-C(acetylene) angles from tetrahedral [mean value 121.3 (2)°].
- Clark, Howard C.,Ferguson, George,Kapoor, Pramesh N.,Parvez, Masood
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p. 3924 - 3928
(2008/10/08)
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- PREPARATION AND REACTIONS OF trans- (R = Me, Ph or C6H4Me-p)
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Formation of trans- (R=Me, Ph or C6H4Me-p) has been achieved by the oxidative addition of ClCH2SR to (PPh3)4Pt in refluxing PhH.The reaction of ClCH2SMe with (PMe2Ph)4Pt led to cis-.The reaction of trans-(PPh3)2Pt(CH2S
- McPherson, Helen,Wardell, James L.
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p. 261 - 266
(2007/10/02)
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- Transfer of Cyclopentadienyl Groups between Platinum Atoms
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Replacement of a chloride ion of cis- (PR3 = tertiary phosphine) by a cyclopentadienyl group from Tl(C5H5) or Hg(C5H5)2 results exclusively in the isomers of with C5H5 trans to PR3.The second chloride can be replaced when excess Tl(C5H5) is used.The ?-bonded cyclopentadienyl groups of either mono- or di-substituted compounds can readily exchange in solution with a chloride of cis- again producing exclusively the same isomers of .The cyclopentadienyl groups do not transfer as fast as chloride ions between the same species, but do so considerably faster than any accompanying CO scrambling processes.Cyclopentadienyl groups from the ?-bonded complexes, and from 5-C5H5)(PR3)2>Cl, can also be readily transferred to mercury when treated with HgCl2.
- Cross, Ronald J.,McLennan, Alistair
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p. 359 - 362
(2007/10/02)
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- Substitution and Isomerisation Reactions at Platinum(II) involving Halide, Tertiary Phosphine, Carbonyl, and Isonitrile Ligands
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Carbon monoxide catalyses trans to cis isomerisations of (L = tertiary phosphine) in chloroform solution.The process involves formation of five-co-ordinate intermediates from which halide or tertiary phosphine can be eliminated, giving trans-(1+) or cis- respectively.Structure changes appear to be by pseudo-rotations rather than by consecutive displacements.A number of isonitrile complexes undergo similar reactions.Halide-bridged cations (2+) formed by halide extraction from cis- by Ag(1+) enter rapid (n.m.r. time-scale) exchange processes with the latter complexes at ambient temperatures.Halide elimination from cis- by solvent chloroform appears to initiate the process.The trans isomers do not participate in the exchange.
- Cross, Ronald J.,Phillips, Ian G.
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p. 2261 - 2264
(2007/10/02)
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- Evidence for Asymmetrical Cleavage of Halide-bridged Platinum(II) Complexes by Nucleophiles
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The addition of PMe2Ph to at low temperatures produces the ions (1+) and (1-) as major products, as well as some of the expected .It is argued that the ionic species result from two molecules of the attacking nucleophile adding to a single platinum atom of the dimer, instead of the more common symmetrical attack.Less ionic product is produced from the addition of PBu3 to and PMe2Ph to , and none at all was detected from the addition of PBu3 to , so the nature of the phosphines involved has a profound effect on the course of the reactions.The ionic materials are able to undergo rapid phosphine exchange even at -60 deg C if excess ligand (PR3 or Cl-) is present.These exchange reactions can complicate the range of products observed unless precautions are taken to prevent local accumulations of the phosphine in the course of mixing the reactants.
- Cross, Ronald J.,Phillips, Ian G.
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p. 2132 - 2136
(2007/10/02)
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