25398-76-9

Upstream product

• 10199-34-5 bis(triphenylphosphine)platinum(II) dichloride 
• 1663-45-2 1,2-bis-(diphenylphosphino)ethane 
• 113948-64-4 Pt(PhCHCH₂)3 
• 83095-83-4 [platinum(II)dichloride(1,2-bis(diphenylphosphino)ethane)] 
• 59329-00-9 {1,3-bis(diphenylphosphino)propane}platinumCl₂ 
• 33012-06-5 Pt(η3-CH2CMeCH2)(acac) 
• 14647-25-7 [Pt(dppe)Cl₂] 
• 2071-20-7 bis-diphenylphosphinomethane 
• 916769-14-7 P(C₆H₅)2CH₂CH(CN)CH₂CH₂CN 
• 5032-65-5 (2-cyanoethyl)diphenylphosphine 
• 406462-91-7 (Ph2P(O)(CH2)3PPh2)Pt(η2-ethylene) 
• 12120-15-9 ethylenebis(triphenylphosphine)platinum⁽⁰⁾ 
• 83571-74-8 (Ph2PCH2CH2PPh2)Pt(η-C2H4) 
• 1008519-04-7 (1,2-bis(diphenylphosphino)ethane)bis(1-pentenyl)platinum(II) 

Downstream Products

• 1361309-89-8 [Pt(dppe)(2-pyridyltellurolate)2] 
• 532438-66-7 [Pt(dppe)(2-Te-C₅H₃(3-Me)N)2] 
• 282731-82-2 (1,2-bis(diphenylphosphanyl)ethane)(tetraselenido-Se,Se)platinum 

Relevant academic research and scientific papers

Heteroleptic Chini-Type Platinum Clusters: Synthesis and Characterization of Bis-Phospine Derivatives of [Pt3n(CO)6n]2- (n = 2-4)

The reactions of [Pt3n(CO)6n]2- (n = 2-4) homoleptic Chini-type clusters with stoichiometric amounts of Ph2PCH2CH2PPh2 (dppe) result in the heteroleptic Chini-type clusters [Pt6(CO)10(dppe)]2-, [Pt9(CO)16(dppe)]2-, and [Pt12(CO)20(dppe)2]2-. Their formation is accompanied by slight amounts of neutral species such as Pt4(CO)4(dppe)2, Pt6(CO)6(dppe)3, and Pt(dppe)2. A similar behavior was observed with the chiral ligand R-Ph2PCH(Me)CH2PPh2 (R-dppp), and two isomers of [Pt9(CO)16(R-dppp)]2- were identified. All the new species were spectroscopically characterized by means of IR and 31P NMR, and their structures were determined by single-crystal X-ray diffraction. The results obtained are compared to those previously reported for monodentate phosphines, that is, PPh3, as well as more rigid bidentate ligands, that is, CH2C(PPh2)2 (P^P), CH2(PPh2)2 (dppm), and o-C6H4(PPh2)2 (dppb). From a structural point of view, functionalization of anionic platinum Chini clusters preserves their triangular Pt3 units, whereas the overall trigonal prismatic structures present in the homoleptic clusters are readily deformed and transformed upon functionalization. Such transformations may be just local deformations, as found in [Pt9(CO)16(dppe)]2-, [Pt9(CO)16(R-dppp)]2-, [Pt12(CO)22(PPh3)2]2-, and [Pt9(CO)16(PPh3)2]2-; an inversion of the cage from trigonal prismatic to octahedral, as observed in [Pt6(CO)10(dppe)]2- and [Pt6(CO)10(PPh3)2]2-; the reciprocal rotation of two trigonal prismatic units with the loss of a Pt-Pt contact as found in [Pt12(CO)20(dppe)2]2-.

Photoinduced net [2 + 2 + 2] cycloreversion of platinum(II) glycolate complexes: A new approach to the generation of reduced, coordinatively unsaturated metal species and the activation of carbohydrate carbon-carbon single bonds

Photolysis of thermally stable (1,2-bis(diphenylphosphino)ethane)platinum(II) glycolate complexes causes a facile net [2 + 2 + 2] cycloreversion of the 2,5-dioxaplatinacyclopentane moiety to give two organic carbonyl compounds and a reactive (dppe)Pt0 intermediate, as shown by trapping with dppe, ethylene, or hydrogen. Photolysis under hydrogen in the presence of (PPh3)4RuH2 leads to hydrocracking of the glycol carbon-carbon single bond.

Transition metal chemistry of low valent group 13 organyls

The coordination of low-valent group 13 organyls EIR [E = Al, Ga, In; R = Cp*, C(SiMe3)3] to transition metals has attracted increasing interest over the past decade. Complexes and cluster compounds of these new ligands with a number of transition metals have been isolated and characterised. The EIR moiety is formally isolobal with CO and PR3 (R = alkyl, Cp*) or carbenes (R = chelating group) with varying σ-donor and π-acceptor properties depending on the organic group R as well as the group 13 metal E. In this review, different ways of forming M-E bonds such as substitution reactions of labile ligands or insertion of EIR into transition metal halide bonds are described. Furthermore, the reactivity of homoleptic complexes Ma(EIR) b, is discussed, outlining the use of these new complex types in bond activation reactions. Wiley-VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany, 2004.

Chemistry of o-Xylidene-Metal Complexes. Part 1. o-Xylidene-magnesium Reagents as Metallocyclic Precursors and Synthesis of (cod = cyclo-octa-1,5-diene); the X-Ray Crystal Structure of the Macrometallocycle 3>

A high yield sythesis of a tetrahydrofuran (thf) solution of the di-Grignard reagent (A) derived from o-bis(chloromethyl)benzene is described, as well as that of an analogue obtained from 1,2-bis(chloromethyl)-4,5-dimethylbenzene.Cooling (A) to ca. -40 deg C yields the colourless chloride-free Mg(CH2C6H4CH2-o)(thf) of unknown structure, whereas at ambient temperature a concentrated solution ( > ca. 0.1 mol dm-3) slowly (days) deposits colourless needles of 3>.A single-crystal X-ray structure determination of the latter (R=0.054 for 1117 'observed' reflections at 295 K) shows it to be trimer.Crystals are orthorhombic, space group F2dd, with a=24.706(8), b=8.948(3), c=44.315(9) Angstroem, and Z=8; the trimeric unit lies on a crystallographic two-fold axis.Each of the three magnesiums is bridged to the other two by a -CH2C6H4CH2-o ligand, the pseudo tetrahedral co-ordination about each magnesium atom being completed by a pair of thf molecules.The utility of the di-Grignard reagent as a general metallocycle precursor is illustrated by the synthesis of (cod=cyclo-octa-1,5-diene) from .In contrast with 2> (dppe=Ph2PCH2CH2PPh2, tmen=Me2NCH2CH2NMe2) affords .

Homo- and heteroleptic complexes of four-membered group 13 metal(I) N-heterocyclic carbene analogues with group 10 metal(0) fragments

A series of complexes between recently developed four-membered group 13 metal(I) heterocycles and group 10 metal(0) fragments have been prepared and structurally characterized. One prepared complex, [Pt{Ga[N(Ar)] 2CNCy2}3] (Ar = C6H 3Pri2-2,6; Cy = cyclohexyl), possesses the shortest Pt-Ga bonds yet reported, the covalent components of which are suggested by theoretical studies to have significant π character.

Thermolysis studies on platinacycloalkane complexes

Thermal decomposition studies on platinacycloalkanes of the type Pt(CH 2)mL2 (where m = 6,7,8,10 and L2 = dppp {1,3-bis(diphenylphosphino)propane}, dppe {1,2-bis(diphenylphosphino) ethane} or L = PPh3, tBu3P) are described. The results reveal that the organic product distribution depends on various factors such as the nature of ligand, the metal system, the mode of decomposition, the ring size and the temperature. Possible mechanistic pathways for the formation of various products are discussed. These platinacycloalkanes can be used as models for metallacycloalkane intermediates in catalytic reactions.

Syntheses of mono- and dinuclear silylplatinum complexes bearing a diphosphino ligand via stepwise bond activation of unsymmetric disilanes

Zero-valence platinum complex [Pt(dppe)(η2-C 2H4)] (1, dppe = 1,2-bis(diphenylphosphino)ethane) treated with disilanes HR1R2SiSiMe3 (a, R1 = R2 = Me; b, R1 = R2 = Ph; c, R1 = H, R2 = Ph) afforded the corresponding disilanylplatinum hydrides [Pt(dppe)(H)(SiR1R2SiMe3)] (2a-c) by oxidative addition of the Si-H bond to the platinum center. The 1,2-silyl migration in 2a,b led to the formation of bis(silyl)platinum complexes [Pt(dppe)(SiHR 1R2)(SiMe3)] (3a,b) with a first-order rate constant of 7.2(2) × 10-4 s-1 at 25°C for 2a and 3.86(4) × 10-4 s-1 at 40°C for 2b, whereas 2c with R1 = H followed by the transient generation of 3c dimerized rapidly to give the bis(μ-silylene)diplatinum complex [Pt(dppe)(μ-SiHPh)] 2 (4c) in a mixture of cis/trans isomers. Heating of the toluene solution of 3b at 100°C resulted in a similar dimerization to 4b. In addition, a trinuclear platinum complex [Pt3(dppe) 3(μ3-SiPh)2] (5) with a trigonal bipyramidal Pt3Si2 core arose from the reaction of 4c with 1 at 60°C in toluene. Unsymmetric disilanes therefore accomplished the syntheses of various monomeric and dimeric platinum complexes via 1,2-hydrogen and silyl migration to the platinum center. The Royal Society of Chemistry.

On the reactivity of alkylthio bridged 44 CVE triangular platinum clusters: Reactions with bidentate phosphine ligands

The 44 cve (cluster valence electrons) triangular platinum clusters [{Pt(PR3)}3(μ-SMe)3]Cl (PR3 = PPh3, 2a; P(4-FC6H4)3, 2b; P(n-Bu)3, 2c) were found to react with PPh2CH 2PPh2 (dppm) in a degradation reaction yielding dinuclear platinum(I) complexes [{Pt(PR3)}2(μ-SMe)(μ-dppm)]Cl (PR3 = PPh3, 3a; P(4-FC6H4) 3, 3b; P(n-Bu)3; 3e) and the platinum(II) complex [Pt(SMe)2(dppm)] (4), whereas the addition of PPh2CH 2CH2PPh2 (dppe) to cluster 2a afforded a mixture of degradation products, among others the complexes [Pt(dppe) 2] and [Pt(dppe)2]Cl2. On the other hand, the treatment of cluster 2a with PPh2CH2CH2CH 2PPh2 (dppp) ended up in the formation of the cationic complex [{Pt(dppp)}2(μ-SMe)2]Cl2 (5). Furthermore, the terminal PPh3 ligands in complex 3a proved to be subject to substitution by the stronger donating monodentate phosphine ligands PMePh2 and PMe2Ph yielding the analogous complexes [{Pt(PR3)}2(μ-SMe)(μ-dppm)]Cl (PR3 = PMePh2, 3c; PMe2Ph, 3d). NMR investigations on complexes 3 showed an inverse correlation of Tolmans electronic parameter ? with the coupling constants 1J(Pt,P) and 1J(Pt,Pt). All compounds were fully characterized by means of NMR and IR spectroscopy. X-ray diffraction analyses were performed for the complexes [{Pt{P(4-FC6H 4)3}}2(μ-SMe)(μ-dppm)]Cl (3b), [Pt(SMe)2(dppm)] (4), and [{Pt(dppp)}2(μ-SMe) 2]Cl2 (5).

P-C and C-C bond formation by Michael addition in platinum-catalyzed hydrophosphination and in the stoichiometric reactions of platinum phosphido complexes with activated alkenes

We recently proposed a new mechanism for platinum-catalyzed hydrophosphination of activated alkenes, in which nucleophilic attack of a phosphido ligand in the intermediate hydride complex Pt(diphos)(PR 2)-(H) (1) on the alkene H2C=CH(X) (X = CN or CO 2R) gave the zwitterion Pt(diphos)(H)(PR2CH 2CHX) (2), containing a cationic Pt center and a phosphine ligand with a pendent stabilized carbanion. Subsequent C-H bond formation involving the Pt-H and the carbanion would yield the product R2PCH 2CH2X (3) and regenerate the catalyst, while attack of the carbanion on another alkene would yield byproducts derived from more than one alkene, such as R2P(CH2CH(X))nCH 2CH2X (7). Several tests of this mechanism and related pathways for product and byproduct formation were investigated. Attempts to trap the proposed carbanion with another electrophile led to the development of a Pt-catalyzed three-component coupling of secondary phosphines, tert-butyl acrylate, and benzaldehyde, yielding the functionalized phosphines R 2PCH2CH(CO2t-Bu)(CHPh(OH)) (R2P = Ph2P (10a); R2P = Me(Is)P (10b, Is = 2,4,6-(i-Pr) 3C6H2)). Reactions of the complexes Pt(diphos)(R′)(PR2) (diphos = (R,R)-Me-Duphos, R′ = Me, PR2 = PPh2 (11), PPh(i-Bu) (12); R′ = Ph, PR 2 = PMeIs (13); diphos = dppe, R' = Me, PR2 = PPh 2 (14), PPh(i-Bu) (15)), models for 1, with tert-butyl acrylate or acrylonitrile gave mixtures of products including Pt-(diphos)(R′)(CH(X) CH2PR2) (A, X = CO2t-Bu or CN), Pt(diphos)(R′)(CH(X)CH2CH(X)CH2PR2) (B), R2PCH2CH2X (3), R2P(CH 2CH(X))n(CH2CH2X) (7), and, in some cases, the dinuclear phosphido-bridged cations [(Pt(diphos)(Me)) 2(μ-PR2)]+ (17). When tert-butanol or water was added to these reactions, more of the phosphines 3 and 7, and less of the intermediates A and B, were formed. Decomposition of A and B gave unidentified platinum dialkyls (C), tentatively formulated as Pt(diphos)(R′)(CH(X) R″). The complex Pt(dppe)(Me)(CH(Me)CO2t-Bu) (21), a model for A, B, and C, was generated either from Pt(dppe)(Cl)-(CH(Me)CO2t-Bu) (20) and ZnMe2 or from Pt(dppe)(Me)(Cl) (19) and ZnBr(CH(Me)CO 2t-Bu)·THF; complexes 20 and 21 did not react with tert-butyl acrylate. These observations are consistent with the proposed nucleophilic mechanism for P-C and C-C bond formation.

Water-promoted reaction of a platinum(II) oxo complex with ethylene

Treatment of [(dppp)Pt(μ-O)]2(LiOTf)2 (dppp = Ph2P(CH2)3PPh2) with ethylene in the presence of trace amounts of water results in oxygen atom transfer to one arm of the bidentate phosphine ligand and formation of(dpppO)Pt(η2-CH2=CH2)2 (dpppO = Ph2P(CH2)3P(O)-Ph2). Further investigation reveals that the reaction of [L2Pt(μ-O)]2(LiOTf)2 with water forms (dppp)Pt(OH)2, which acts as a catalyst for the oxygen atom transfer reaction. The analogous oxo complex [(PPh3)2Pt(μ-O)]2-(LiBF4)2 does not react with ethylene under similar conditions. These results indicate that hydroxo complex intermediates should be considered in oxygen atom transfer reactions.