15692-07-6Relevant academic research and scientific papers
Photoreduction of Pt(IV) chloro complexes: Substrate chlorination by a triplet excited state
Perera, Tharushi A.,Masjedi, Mehdi,Sharp, Paul R.
supporting information, p. 7608 - 7621 (2014/08/05)
The Pt(IV) complexes trans-Pt(PEt3)2(Cl) 3(R) 2 (R = Cl, Ph, 9-phenanthryl, 2-trifluoromethylphenyl, 4-trifluoromethylphenyl, 3-perylenyl) were prepared by chlorination of the Pt(II) complexes trans-Pt(PEt3)2(R)(Cl) 1 with Cl 2(g) or PhICl2. Mixed bromo-chloro complexes trans,trans-Pt(PEt3)2(Cl)2(Br)(R) (R = 9-phenanthryl, 4-trifluoromethylphenyl), trans,cis-Pt(PEt3) 2(Cl)2(Br)(4-trifluoromethylphenyl), trans,trans- Pt(PEt3)2(Br)2(Cl)(R) (R = 9-phenanthryl), and trans,cis-Pt(PEt3)2(Br)2(Cl)(4- trifluoromethylphenyl) were obtained by halide exchange or by oxidative addition of Br2 to 1 or Cl2 to trans-Pt(PEt3) 2(R)(Br). Except for 2 (R = Ph, 4-trifluoromethylphenyl), all of the Pt(IV) complexes are photosensitive to UV light and undergo net halogen reductive elimination to give Pt(II) products, trans-Pt(PEt3) 2(R)(X) (X = Cl, Br). Chlorine trapping experiments with alkenes indicate a reductive-elimination mechanism that does not involve molecular chlorine and is sensitive to steric effects at the Pt center. DFT calculations suggest a radical pathway involving 3LMCT excited states. Emission from a triplet is observed in glassy 2-methyltetrahydrofuran at 77 K where photoreductive elimination is markedly slowed.
A dynamic disorderlinked reversible phase transition in a new chloroform solvate of cisdichloridobis(triethylphosphane)platinum(II)
Dillon, Keith B.,Howard, Judith A. K.,Monks, Philippa K.,Probert, Michael R.,Shepherd, Helena J.
, p. m111-m114 (2011/06/09)
The title compound, cisdichloridobis(triethylphosphane)platinum(II) chloroform monosolvate, [PtCl2(C6H15P) 2]·CHCl3, has been obtained from ligand scrambling in the cis-[PtCl2(Cyp2PCl)(PEt3)] (Cyp = cyclopentyl) system in CHCl3 solvent. Unlike the two previously reported unsolvated polymorphs, which are both monoclinic, the compound crystallizes in an orthorhombic setting. Furthermore, the system exhibits a reversible temperaturedependent structural phase transition, coupling a reduction in anisotropic displacement parameters and a reduction in crystallographic symmetry on cooling. The hightemperature phase adopts space group Pnma with the complex and solvent molecules sitting across a crystallographic mirror plane (Z′ = 0.5). The low-temperature phase adopts the space group P212121 with Z′ = 1.
Towards a catalytic hydrogenolysis of silicon-silicon bonds: Formation of Si-H bonds from disilanes and H2 at platinum
Roscher, Anja,Bockholt, Andreas,Braun, Thomas
, p. 1378 - 1382 (2009/06/06)
Reactions of the disilanes Cl2MeSiSiMeCl2, ClMe 2SiSiMe2Cl and Me3SiSiMe3 led to the products of oxidative addition cis-[Pt(SiMeCl2)2(PEt 3)2] (2
Reactions of R2P-P(SiMe3)2 with [(R3′ P)2 PtCl2]. Syntheses and structures of [μ2-(1,2:2-η-P2){Pt(PEt3) 2}2{Pt(PEt3
Domańska-Babul, Wioleta,Chojnacki, Jaroslaw,Matern, Eberhard,Pikies, Jerzy
, p. 3640 - 3648 (2008/02/08)
Full title: Reactions of R2P-P(SiMe3)2 with [(R3′ P)2 PtCl2]. Syntheses and structures of [μ2-(1,2:2-η-P2){Pt(PEt3) 2}2{Pt(
Multiple coordination modes of hemilabile 3-dimethylaminopropyl chalcogenolates in platinum(II) complexes: Synthesis, spectroscopy and structures
Dey, Sandip,Jain, Vimal K.,Butcher, Ray J.
, p. 2653 - 2660 (2008/10/09)
The reactions of N,N-dimethylaminopropyl chalcogenolates with platinum(II) compounds have been carried out and complexes of the types [PtCl(ECH2CH2CH2NMe2)]2 (1) (E = S (1a) and Se (1b)), [Pt(ECH2CH2CH2NMe2)2]n (2) (E = S (2a) and Se (2b)), [(PtCl2)2{(Me2NCH2CH2CH2E)2}]n (3), [PtX(SeCH2CH2CH2NMe2)]2 (4) (X = SePh (4a) and OAc (4b)) and [PtCl(ECH2CH2CH2NMe2)(PR3)]n (5) (E = S, Se, Te) have been isolated. These complexes have been characterized by elemental analysis, IR, UV-Vis, NMR (1H, 13C, 31P, 77Se, 195Pt) spectroscopy and FAB mass spectral data. The structures of [PtCl(SeCH2CH2CH2NMe2)]2 (1b) and [PtCl(SCH2CH2CH2NMe2)(PPr3)]2 (5a) have been established by single crystal X-ray diffraction data. Both the molecules have dimeric structures. In 1b, two platinum atoms are held together by symmetrically bridging Se atoms of the chelating selenolate groups. In 5a, two thiolates form a four-membered Pt2S2 bridge with dangling NMe2 groups.
Homo- and hetero-, bi- and tri-nuclear palladium(II) and platinum(II) complexes containing single bridging chalcogenolate of a metallo-ligand, [MCl(ECH2CH2NMe2)(PR3)] (M = Pt, Pd; E = Se, Te)
Dey, Sandip,Jain, Vimal K.,Butcher, Ray J.
, p. 1385 - 1390 (2008/10/09)
Bi- and tri-nuclear palladium/platinum complexes of the types [MCl(ECH2CH2NMe2)(PR3)M′Cl2(PR3)] (M, M′ = Pd or Pt) and [{PtCl(SeCH2CH2NMe2)(PR3)}2M′ Cl2] (M′ = Pd or Pt; PR3 = PEt3 or PPr3n) have been prepared. All complexes were characterized by elemental analysis, NMR (1H, 31P, 77Se, 125Te, 195Pt) data. The structures of [PdCl(SeCH2CH2NMe2)(PPh3)PtCl2(PPh3)] and [{PtCl(SeCH2CH2NMe2)(PEt3)}2PtCl2] have been established by single crystal X-ray diffraction analysis. In the latter complex, three square planar platinum atoms are held together by the single bridging selenolate group in an almost linear chain arrangement.
1,1,2,2-tetramethyl-1,2-bis(phenylthiomethyl)disilane, a flexible ligand for the construction of macrocyclic, mesocyclic, and bridged dithioether complexes. Synthesis of the bis-silylated olefins Z-(PhSCH2)Me 2SiC(H)=C(Ar)SiMe2(CH2SPh) by catalytic activation of the Si-Si bond
Peindy, Harmel N.,Guyon, Fabrice,Jourdain, Isabelle,Knorr, Michael,Schildbach, Daniel,Strohmann, Carsten
, p. 1472 - 1479 (2008/10/09)
The functionalized disilane (PhSCH2)Me2SiSiMe 2(CH2SPh) (1) has been prepared and coordinated as a dithioether ligand on [PtCl2(PhCN)2] to afford the fluxional seven-membered chelate complex cis-[PtCl2{(PhSCH 2)2Si2Me4}] (2a). After metathesis reaction of 2a with NaI the diiodo derivative cis-[PtI2{(PhSCH 2)2Si2Me4}] (2b) was obtained. Treatment of [Re(μ-Br)(CO)3THF]2 with 1 equiv of 1 yields the bromo-bridged dinuclear complex fac-[{Re(μ-Br)(CO) 3}2{μ-(PhSCH2)2Si 2Me4}] (5), which is spanned by 1 forming a 10-membered mesocycle. Addition of a further equivalent of 1 yields the dinuclear macrocyclic compound fac-[{ReBr(CO)3}2{μ-(PhSCH 2)2Si2Me4}2] (4), forming a 14-membered ring system. The chloro-bridge of [RuCI(μ-Cl)(CO) 3]2 is cleaved by 1 to give the dinuclear compound fac-[{RuCl2(CO)3}2{μ-(PhSCH 2)2Si2Me4}] (6), in which the two metal fragments are linked by the thioether functions. In the presence of catalytic amounts of Pd(OAc)2/CNR, the Si-Si bond of 1 is cleaved and addition across the triple bond of phenylacetylene or p-tolylacetylene affords the bis-silylated olefins Z-(PhSCH2)Me2SiC(H)=C(Ar) SiMe2(CH2SPh) (7a Ar = Ph; 7b Ar = p-Tol). The new compounds have been studied by multinuclear NMR techniques; the crystal structures of 2a, 2b, 4, 5, 6, and 7a have been determined by X-ray diffraction studies.
Reactions of tBu2P-PLi-PtBu2 with [(Et3P)2MCl2] (M = Ni, Pd, Pt). Synthesis and properties of [(1,2-η-tBu2P=P-PtBu 2)M(PEt3)Cl] (M=Ni, Pd)
Baum, Elke,Matern, Eberhard,Robaszkiewicz, Andrzej,Pikies, Jerzy
, p. 1073 - 1077 (2008/10/09)
tBu2P-PLi-PtBu2·2THF reacts with [cis-(Et3P)2MCl2] (M = Ni, Pd) yielding [(1,2-η-tBu2P=P-PtBu 2)Ni(PEt3)Cl] and [(1,2-η-tBu 2P=P-PtBu2)Pd(PEt3)Cl], respectively. tBu2P-PLi-tPBu2 undergoes an oxidation process and the tBu2P-P-PtBu 2 ligand adopts in the products the structure of a side-on bonded 1,1-di-tert-butyl-2-(di-tert-butylphosphino)diphosphenium cation with a short P-P bond. Surprisingly, the reaction of tBu2P-PLi-P tBu2·2THF with [cis-(Et3P) 2PtCl2] does not yield [(1,2-η-tBu 2P=P-PtBu2)Pt(PEt3)Cl].
Mechanistic insight into the protonolysis of the Pt-C bond as a model for C-H bond activation by platinum(II) complexes
Romeo, Raffaello,D'Amico, Giuseppina
, p. 3435 - 3446 (2008/10/09)
The kinetic and NMR features of the protonolysis reactions on platinum(II) alkyl complexes of the types cis-[PtMe2L2], [PtMe 2(L-L)], cis-[PtMeClL2], and [PtMeCl(L-L)] (L = PEt 3, P(Pri)3, PCy3, P(4-MePh) 3, L-L = dppm, dppe, dppp, dppb) in methanol suggest a rate-determining proton attack at the Pt - C bond. In contrast, a multistep oxidative-addition - reductive-elimination mechanism characterizes the methane loss on protonation of the corresponding trans-[PtMeClL2] species. Tools that were particularly diagnostic in suggesting different reaction pathways for the two systems were (i) the different results of kinetic deuterium isotope experiments, (ii) the detection or absence of Pt(IV) hydrido alkyl intermediate species by low-temperature 1H NMR experiments, and (iii) the detection or absence of isotope scrambling and incorporation of deuterium into Pt - CH3, combined with the loss of a range of CH nDn-4 isotopomers. For all systems, the rates of protonolysis are retarded by ligand steric congestion, accelerated by ligand electron donation, and almost unaffected by the chain length along the series of chelate complexes. A straight line correlates the rates of protonolysis of cis-dialkyl and cis-monoalkyl complexes, the difference in reactivity between the two systems being almost 5 orders of magnitude (slope of the line = 6 × 104). Factors controlling the dichotomy of behavior between complexes of different geometry have been taken into consideration. Application of the principle of microscopic reversibility suggests the reason why platinum complexes with nitrogen donor ligands appear to be far more efficient than platinum phosphane complexes in activating the C-H bond.
Synthesis and characterisation of triselenocarbonate [CSe3] 2- complexes
Burchell, Colin J.,Aucott, Stephen M.,Slawin, Alexandra M. Z.,Woollins, J. Derek
, p. 735 - 739 (2007/10/03)
[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.
