17030-86-3Relevant academic research and scientific papers
Solvent-free mechanochemical synthesis of two Pt complexes: Cis-(PH3P)2PtCl2 and cis-(Ph3P)2PtCO3
Balema, Viktor P.,Wiench, Jerzy W.,Pruski, Marek,Pecharsky, Vitalij K.
, p. 1606 - 1607 (2002)
Cis-(Ph3P)2PtCl2 and cis-(Ph3P)2PtCO3 were prepared mechanochemically from solid reactants in the absence of a solvent; cis-(Ph3P)2PtCl2 was obtained in 98% yield after ball-milling of polycrystalline PtCl2 and Ph3P; the mechanically induced solid-state reaction of cis-(Ph3P)2PtCl2 with an excess of anhydrous K2CO3 produced cis-(Ph3P)2PtCO3 in 70% yield; the formation of transition metal complexes as a result of mechanochemical solvent-free reactions has been confirmed by means of solid-state 31P MAS NMR spectroscopy, X-ray powder diffraction and differential thermal analysis.
Novel reactivity aspects of cis-bis(1-alkenyl)platinum(II) compounds of the type Pt(CH2(CH2)nCHCH2) 2L2 (where L2 = dppp, dppe, dppm and n = 1, 2)
Sivaramakrishna, Akella,Moss, John R.,Su, Hong
, p. 3345 - 3350 (2011/02/16)
We describe the synthesis, structure and reactivity of novel bis(1-alkenyl)platinum(II) complexes, Pt[CH2(CH2) nCHCH2]2L2 (where L2 = dppp, dppe, dppm and n = 1, 2). The stability of the title complexes with the different ligands is discussed. The steric, chelating and electronic properties of the ligands have a significant impact on the structure as well as on the reactivity of the complexes. Novel reactions with elemental sulfur and carbon dioxide are described and discussed.
Heterobimetallic dioxygen activation: Synthesis and reactivity of mixed Cu-Pd and Cu-Pt bis(μ-oxo) complexes
York, John T.,Llobet, Antoni,Cramer, Christopher J.,Tolman, William B.
, p. 7990 - 7999 (2008/02/04)
Heterobimetallic CuPd and CuPt bis(μ-oxo) complexes have been prepared by the reaction of (PPh3)2MO2 (M = Pd, Pt) with LCu(I) precursors (L = β-diketiminate and di- and triamine ligands) and characterized by low-temperature UV-vis, resonance Raman, and 1H and 31P{1H} NMR spectroscopy in conjunction with DFT calculations. The complexes decompose upon warming to yield OPPh3, and in one case this was shown to occur by an intramolecular process through crossover experiments using double-labeling (oxo and phosphine). The reactivity of one of the complexes, LMe2Cu(μ-O)2Pt(PPh 3)2 (LMe2 = β-diketiminate), with a variety of reagents including CO2, 2,4-di-tert-butylphenol, 2,4-di-tert-butylphenolate, [NH4][PF6], and dihydroanthracene, was compared to that of homometallic Pt2 and Cu2 counterparts. Unlike typical [CU2(μ-O) 2]2+ cores which have electrophilic oxo groups, the oxo groups in the [Cu(μ-O)2Pt]+ core behave as bases and nucleophiles, similar to previously described Pt2 compounds. In addition, however, the [Cu(μ-O)2Pt]+ core is capable of oxidatively coupling 2,4-di-terf-butylphenol and 2,4-di-tert-butylphenolate. Theoretical evaluation of the electron affinities, basicities, and H-atom transfer kinetics and thermodynamics of the Cu2 and CuM (M = Pd, Pt) cores showed that the latter are more basic and form stronger O-H bonds.
Preparation and structural characterization of 1,4-digerma-2-buten-1,4- diylplatinum(II) complexes and their reactions with alkynes, carbon monoxide, and isocyanides
Mochida, Kunio,Karube, Hironori,Nanjo, Masato,Nakadaira, Yasuhiro
, p. 4734 - 4741 (2008/10/09)
1,4-Digerma-2-buten-1,4-diylplatinum(II) complexes were prepared by treatment of a (η-ethylene)(triphenylphosphine)platinum(0) complex with (Z)-α,β-bis(dialkylgermyl)styrenes, and their structures were determined by spectroscopic analysis coupled with X-ray diffraction methods. Thermolysis of 1,4-digerma-2-buten-1,4-diylplatinum(II) complexes afforded linear and cyclic trigermanes and a dinuclear platinum complex. The 1,4-digerma-2-buten-1,4-diylplatinum(II) complexes reacted with alkynes to give the corresponding insertion products, cyclic germy(germylvinyl)platinum(II) species, whose structures have been determined by spectroscopic analysis. The cyclic germy(germylvinyl)platinum(II) complexes were found to easily liberate 1,4-digermacyclohexa-2,5-dienes and a platinum(O) complex. The reactions of 1,4-digerma-2-buten-1,4-diylplatinum(II) complexes with carbon monoxide and isocyanides afforded the corresponding platinum complexes containing one carbon monoxide and one isocyanide ligand, respectively.
Syntheses, Spectra, and Structures of (Diphosphine)platinum(II) Carbonate Complexes
Andrews, Mark A.,Gould, George L.,Klooster, Wim T.,Koenig, Kristina S.,Voss, Eric J.
, p. 5478 - 5483 (2008/10/09)
A variety of (diphosphine)platinum(II) carbonate complexes, (LL)Pt(CO3), are readily prepared from the corresponding (diphosphine)platinum dichlorides by treatment with silver carbonate in dichoromethane solution provided that water is present. This reaction also permits facile preparation of analogous 13C-labeled complexes. The carbonate ligands in these complexes have been characterized by IR and 13C NMR spectroscopy. Alternative preparative routes involve conversion of the precursor dichlorides to the corresponding dialkoxides or diphenoxides, followed by treatment with water and carbon dioxide. Various reaction intermediates have been spectroscopically observed in the latter syntheses. Two crystalline modifications of (Ph2PCH2CH2CH2PPh 2)Pt(CO3), one with and one without a dichloromethane of solvation, have been studied by single-crystal X-ray diffraction. Crystal data for PtP2O3C28H26: P21/c, Z = 4, T = 200 K, a = 10.362(8) ?, b = 14.743(6) ?, c = 19.183(10) ?, β = 122.69(6)°. Crystal data for PtP2O3C28H26·CH 2Cl2: P21/c, Z = 4, T ≈ 298 K, a = 11.744(2) ?, b = 15.526(3) ?, c = 15.866(3) ?, β = 101.58(1)°.
Synthesis, Reactions and Structure of a Highly Basic Platinum(II) Di(μ-oxo) Dimer with an Unusual Lithium Tetrafluoroborate Interaction
Li, Wei,Barnes, Charles L.,Sharp, Paul R.
, p. 1634 - 1636 (2007/10/02)
The reaction chemistry and X-ray crystal structure of the platinum(II) oxo complex 2*LiBF4 (L = PPh3) reveal the presence of a highly basic oxo ligand and an unusual oxo-LiBF4 interaction.
Electrochemical generation and reactivity of bis(tertiary phosphine)platinum(0) complexes: A comparison of the reactivity of [Pt(PPh3)2] and [Pt(PEt3)2] equivalents
Davies, Julian A.,Eagle, Cassandra T.,Otis, Deborah E.,Venkataraman, Uma
, p. 1080 - 1088 (2008/10/08)
Electrochemical reduction of cis-[PtCl2(PR3)2] (R = Ph, Et) in CH3CN/C6H6 containing NBu4ClO4 at a Hg pool electrode generates [Pt(PR3)2] equivalents in solution. Where R = Ph, the [Pt(PR3)2] equivalent may be trapped by O2, O2/CO2, HCl, MeI, C6H5COCl, and RC≡CR (R = Ph, COOMe) but not by the less reactive substrate PhCl. Where R = Et, the [Pt(PR3)2] equivalent reacts with the NBu4+ cation to ultimately generate trans-[PtH(Cl)(PEt3)2]. Prolonged electrolyses cause reduction of trans-[PtH(Cl)(PEt3)2] leading to hydride attack on the CH3CN solvent and ultimately forming trans-[PtH(CH2CN)(PEt3)2]. In the presence of bases such as NBu3, trans-[PtH(CH2CN)(PEt3)2] is isomerized in CH3CN solution producing trans-[PtCN(CH3)(PEt3)2]. The use of electroinactive trapping agents such as PhCl or PhCN as cosolvents for the reduction of cis-[PtCl2(PEt3)2] allows trapping of the [Pt(PEt3)2] equivalents as trans-[PtPh-(X)(PEt3)2] (X = Cl, CN).
Further investigations of the reactivity of η2-bonded nitroso complexes of platinum. The crystal structure of Pt(PPh3)2(PhNO)
Pizzotti, Maddalena,Porta, Francesca,Demartin, Francesco,Masciocchi, Norberto
, p. 265 - 278 (2007/10/02)
The crystal structure of Pt(PPh3)2(PhNO) (I) has been determined.This is the first example of a structure determination for a monmeric complex of a metal in a low oxidation state and bearing an η2-bonded nitroso ligand.Compound I crystallizes in the monoclinic space group P21/c (NO. 14) with a 14.228(4), b 13.914(3), c 17.855(4) Angstroem, β 100.31(2) grad, V 3478(3) Angstroem3 and Z = 4.Final R and Rw indices are 0.026 and 0.030 for 3609 observed reflections (I >= 3 ?(I)).The new complexes Pt(PPh3)(RNO) (R = But(II), CF3(III)) have been synthesized and their reactions with CO2, CS2, PhNCO, PhNCS, CO, alkenes and dimethyl acetylenedicarboxylate have been investigated and compared with those of the previously studied compound I.Preliminary observations on the synthesis and reactivity of Pd(PPh3)2(CF3NO) (IV) are also reported.
Metal Complexes with Carbon Sulfides and Selenides as Ligands, XVIII. Conversion of η2-Bonded Heteroallenes (CS2, CSSe, and CSe2) into the Chelate Ligands CS32-, CSSe22-, and C2Se42-
Ebner, Martin,Werner, Helmut
, p. 482 - 487 (2007/10/02)
(PPh3)2Pt(η2-CS2) (1) reacts with PMe3, PMe2Ph, and PMePh2 to produce the (trithiocarbonato-S,S')platinum(II) complexes (PR3)2Pt(η2-S2CS) (2-4).Similarly, on treatment of (PPh3)2Pt(η2-CSSe) with PMe3 the compound (PMe3)2Pt
Electrochemical generation and reactivity of bis(triphenylphosphine)platinum(0): An electrosynthesis of platinum-acetylene complexes
Davies, Julian A.,Eagle, Cassandra T.,Otis, Deborah E.,Venkataraman, Uma
, p. 1264 - 1266 (2008/10/08)
Controlled potential bulk reductive electrolysis of cis-[PtCl2(PPh3)2] results in the generation of [Pt(PPh3)2] in solution. This 2-coordinate, 14-electron compound is efficiently trapped by acetylene
