104413-90-3Relevant articles and documents
Reactivity of hemilabile pyridyl- and methyl-substituted pyrimidylselenolates with [MCl2(dppf)] (M?=?Pd, pt; dppf?=?bis(diphenylphisphino)ferrocene)
Chauhan, Rohit Singh,Cordes, David B.,Slawin, Alexandra M.Z.,Yadav, Seema,Dash, Chandrakanta
, p. 125 - 129 (2018)
The bis(diphenylphisphino)ferrocene (dppf) derived palladium analogue of [PdCl2(dppf)] on reaction with the sodium salt of pyridyl/pyrimidyl selenolate yielded mononuclear cis configured complex [Pd(SeAr)2(dppf)] (Ar = C5H
Substituted Metal Carbonyls. Part 21. as a Metalloligand in Heteropolymetallic Aggregates of AuI, PdII and PtII. Crystal and Molecular Structures of 2> and
Phang, Lai-Tee,Au-Yeung, Steve C. F.,Hor, T. S. Andy,Khoo, Soo Beng,Zhou, Zhong-Yuan,Mak, Thomas C. W.
, p. 165 - 172 (1993)
The complexes behave like a monodentate phosphine ligand and displace the labile ligands from , trans- and cis- (dmso = dimethyl sulfoxide) to yield the corresponding dppf-bridged heteropolymetallic complexes of general formula xy> (M' = Au, x = y = 1; M' = Pd or Pt, x = y = 2).Only the trans isomers have been isolated for PdII and PtII.Isomerisation of the M' = Pt, M = Cr complex to the cis form, followed by partial elimination of to form , after 3d in CDCl3 was revealed by NMR spectroscopy.The solution characteristics of both geometrical isomers of the representative M' = Pt, M = Cr complex have been established by two-dimensional NMR studies.UV-Photolytic degradation of the M' = Pd or Pt, M complexes generally gave , , and .The molecular structures of trans-2> and have been determined.The former represents a trimetallic pentanuclear aggregate and the latter a metalloligand with a pendant phosphine on a bimetallic complex.Cyclic voltammetry of all the complexes has been examined and generally reveals one chemically reversible phosphinoferrocene-based oxidation, followed by an irreversible oxidation of the complex.
Aromatic amine N-oxide organometallic compounds: Searching for prospective agents against infectious diseases
Rodrguez Arce, Esteban,Mosquillo, M. Florencia,Prez-Daz, Leticia,Echeverra, Gustavo A.,Piro, Oscar E.,Merlino, Alicia,Coitio, E. Laura,Marngolo Ribeiro, Camila,Leite, Clarice Q. F.,Pavan, Fernando R.,Otero, Luca,Gambino, Dinorah
, p. 14453 - 14464 (2015)
In search of prospective agents against infectious diseases, 1,1′-bis(diphenylphosphino)ferrocene pyridine-2-thiolato-1-oxide M(II) hexafluorophosphate compounds [M(mpo)(dppf)](PF6), where M = palladium or platinum, were synthesized and fully characterized in the solid state and in solution using experimental and DFT computational techniques. The compounds are isomorphous and the M(II) transition metal ions are in a nearly planar trapezoidal cis-coordination bound to the pyridine-2-thiolato-1-oxide (mpo) and to the 1,1′-bis(diphenylphosphino)ferrocene molecules, both acting as bidentate ligands. Both compounds showed high cytotoxic activity on Trypanosoma cruzi and Mycobacterium tuberculosis (MTB) and acceptable selectivities towards MTB, but good to excellent selectivity index values as anti-T. cruzi compounds. The inclusion of the ferrocene moiety (dppf ligand) improved the selectivity towards the parasite when compared to the previously reported [M(mpo)2] complexes. Related to the probable mechanism of action of the complexes, molecular docking studies on modelled T. cruzi NADH-fumarate reductase (TcFR) predicted that both be very good inhibitors of the enzyme. The effect of the compounds on the enzyme activity was experimentally confirmed using T. cruzi protein extracts. According to all obtained results, both [M(mpo)(dppf)](PF6) compounds could be considered prospective anti-trypanosomal agents that deserve further research.
Combining ferrocenes and molecular squares: Self-assembly of heterobimetallic macrocyclic squares incorporating mixed transition metal systems and a main group element. Single-crystal X-ray structure of [Pt(dppf)(H2O)2][OTf]2
Stang, Peter J.,Olenyuk, Bogdan,Fan, Jun,Arif, Atta M.
, p. 904 - 908 (1996)
The preparation of the reactive diaqua complexes of (bis(diphenylphosphino)ferrocene)-palladium(II) and -platinum(II) bis(triflates) and the X-ray crystal structure of [Pt(dppf)-(H2O)2][OTf]2 (dppf = 1,1′-bis(diphenylphosphino)ferrocene) are reported. Interaction of these complexes with 2,7-diazapyrene produced novel octanuclear square-shaped metallomacrocycles. Modular self-assembly of [Pd(dppf)H2O)2][OTf]2 and [Pt(dppf)H2O)2][OTf]2 with bis-[4-(4′-pyridyl)phenyl]iodonium triflate results in the facile formation of hexanuclear macrocyclic squares with alternating iodonium-late transition metals (Pd(II) or Pt(II)) at the corners and ferrocene complex as the chelating unit.
Highly Active Platinum Catalysts for Nitrile and Cyanohydrin Hydration: Catalyst Design and Ligand Screening via High-Throughput Techniques
Xing, Xiangyou,Xu, Chen,Chen, Bo,Li, Chengcheng,Virgil, Scott C.,Grubbs, Robert H.
supporting information, p. 17782 - 17789 (2019/01/04)
Nitrile hydration provides access to amides that are indispensable to researchers in chemical and pharmaceutical industries. Prohibiting the use of this venerable reaction, however, are (1) the dearth of biphasic catalysts that can effectively hydrate nitriles at ambient temperatures with high turnover numbers and (2) the unsolved challenge of hydrating cyanohydrins. Herein, we report the design of new "donor-acceptor"-type platinum catalysts by precisely arranging electron-rich and electron-deficient ligands trans to one other, thereby enhancing both the nucleophilicity of the hydroxyl group and the electrophilicity of the nitrile group. Leveraging a high-throughput, automated workflow and evaluating a library of bidentate ligands, we have discovered that commercially available, inexpensive DPPF [1,1′-ferrocenendiyl-bis(diphenylphosphine)] provides superior reactivity. The corresponding "donor-acceptor"-type catalyst 2a is readily prepared from (DPPF)PtCl2, PMe2OH, and AgOTf. The enhanced activity of 2a permits the hydration of a wide range of nitriles and cyanohydrins to proceed at 40 °C with excellent turnover numbers. Rational reevaluation of the ligand structure has led to the discovery of modified catalyst 2c, harboring the more electron-rich 1,1′-bis[bis(5-methyl-2-furanyl)phosphino] ferrocene ligand, which demonstrates the highest activity toward hydration of nitriles and cyanohydrins at room temperature. Finally, the correlation between the electron-donating ability of the phosphine ligands with catalyst efficiencies of 2a, 2c, 2d, and 2e in the hydration of nitrile 7 are examined, and the results support the "donor-acceptor" hypothesis.
Tin(II) halide insertion or halogen exchange in the reactions of dihaloplatinum(II) complexes with tin(II) halide
Momeni, Badri Z.,Kazmi, Hoori,Najafi, Atefeh
, p. 1618 - 1627 (2011/10/31)
Reactions of SnCl2 with the complexes cis-[PtCl 2(P2)] (P2=dppf (1,1′- bis(diphenylphosphino)ferrocene), dppp (1,3-bis(diphenylphosphino)propane=1, 1′-(propane-1,3-diyl)bis[1,1-diphenylphosphine]), dppb (1,4-bis(diphenylphosphino)butane=1,1′-(butane-1,4-diyl)bis[1, 1-diphenylphosphine]), and dpppe (1,5-bis(diphenylphosphino)pentane=1,1′- (pentane-1,5-diyl)bis[1,1-diphenylphosphine])) resulted in the insertion of SnCl2 into the Pt-Cl bond to afford the cis-[PtCl(SnCl 3)(P2)] complexes. However, the reaction of the complexes cis-[PtCl2(P2)] (P2=dppf, dppm (bis(diphenylphosphino)methane=1,1′-methylenebis[1,1-diphenylphosphine]), dppe (1,2-bis(diphenylphosphino)ethane=1,1′-(ethane-1,2-diyl)bis[1,1- diphenylphosphine]), dppp, dppb, and dpppe; P=Ph3P and (MeO) 3P) with SnX2 (X=Br or I) resulted in the halogen exchange to yield the complexes [PtX2(P2)]. In contrast, treatment of cis-[PtBr2(dppm)] with SnBr2 resulted in the insertion of SnBr2 into the Pt-Br bond to form cis-[Pt(SnBr3) 2(dppm)], and this product was in equilibrium with the starting complex cis-[PtBr2(dppm)]. Moreover, the reaction of cis-[PtCl 2(dppb)] with a mixture SnCl2/SnI2 in a 2 : 1 mol ratio resulted in the formation of cis-[PtI2(dppb)] as a consequence of the selective halogen-exchange reaction. 31P-NMR Data for all complexes are reported, and a correlation between the chemical shifts and the coupling constants was established for mono- and bis(trichlorostannyl) platinum complexes. The effect of the alkane chain length of the ligand and SnII halide is described. Copyright
Synthesis and characterisation of 2,2-bis(hydroxymethyl)-1,3-diselenolato metal(II) complexes bearing various phosphanes
Niksch, Tobias,Goerls, Helmar,Friedrich, Manfred,Oilunkaniemi, Raija,Laitinen, Risto,Weigand, Wolfgang
, p. 74 - 94 (2010/04/01)
An improved synthesis of 4,4-bis(hydroxymethyl)-1,2-diselenolane and the complexation properties of the corresponding diselenolato dianion to group-10 metals are reported. We describe an efficient and straightforward procedure that bypasses the isolation of the malodorous and airsensitive diselenol and starts with the diselenide appropriate group-10 metal complex bearing phosphane and chlorido ligands. A series of complexes with various monoand bidentate phosphanes is prepared and characterised by multinuclear NMR spectroscopy, mass spectrometry, and elemental analysis. Furthermore, the structure of most complexes is studied by single-crystal X-ray diffraction to establish their supramolecular arrangement in the solid state. Consequently, several group-10 metal complexes with P-M-P angles (bite angles) in the range from 71-108° are investigated. The use of the sterically demanding bridging phosphane 4,5-bis(diphenylphosphanyl)-9,9-dimethylxanthene, which exhibits a large bite angle yields a mixture of a di- and trinuclear complex. While the platinum-containing complexes are proven to be rather stable, the palladium and nickel analogues tend to decompose. Especially, the nickel complexes were found to be sensitive against: oxidation. This circumstance leads to the formation of the so far unknown 1,8-bis(diphenylphosphanyl)naphthalene monooxide, the formation and structure of which could be confirmed from NMR spectroscopic data and single-crystal X-ray diffraction.
Group 8 and 10 hyponitrite and dinitrosyl complexes
Arulsamy, Navamoney,Bohle, D. Scott,Imonigie, Jerome A.,Moore, Raecca C.
, p. 4737 - 4745 (2008/10/09)
cis-Hyponitrite complexes LnM(N2O2) (M = Ni, Pt; Ln = PPh3, PPh2Me, dppe, and dppf) of divalent group 10 metals have been previously shown to be readily prepared by treating the corresponding LnMCl2 derivatives with sodium-(Z)-1-{4-(2,6-di-tert-butyl-4-methoxycyclohexadienonyl)}diazen-1-ium-1,2-diolate. These complexes adopt a diamagnetic square planar geometry with oxygen bound chelating planar cis-hyponitrite ligands. They are readily prepared at room temperature but thermally decompose above 90 °C with release of nitrous oxide. Electrophiles such as iodine, methyltriflate, and hydrochloric acid also react rapidly with the cis-hyponitrite complexes to give nitrous oxide. The structure of one of these previously prepared complexes, (PPh3)2Pt(N2O2), has been redetermined at -100 °C as a dichloromethane solvate with improved precision. The related tetrahedral group 8 dinitrosyl complexes, (PPh3)2M(NO)2 (M = Ru, Os; Ln = PPh3, dppe, and dppf) have been reexamined and new derivatives with chelating phosphines have been prepared by ligand substitution on the corresponding (PPh3)2M(NO)2. The structures of Ru(dppf)(NO)2 and Os(dppe)(NO)2 have been determined. These two analogous families of cis-hyponitrite and dinitrosyl complexes illustrate the balance of metal dn electron count and nitrosyl redox state with one having linear nitrosyls bound to low valent metal centers, and the former having coupled N2 O22 - ligands bound to a higher oxidation state metal center.
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.
Synthesis and characterisation of cyanodithioimidocarbonate [C2N2S2]2- complexes
Burchell, Colin J.,Aucott, Stephen M.,Milton, Heather L.,Slawin, Alexandra M.Z.,Woollins, J. Derek
, p. 369 - 374 (2007/10/03)
[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.
