1,721,105 research outputs found
Risultati del I confronto interlaboratorio nazionale di spettroscopia 1H NMR organizzato da Retelab: verso la promozione di metodi ufficiali?
No full textSpecial Issue: Novel Approaches for the Analytical Evaluation of Food Quality and Authenticity
Full text linkN-substituted bis(diphenylphosphanyl)amine ligands bearing the thioether functional group: coordination modes in PtCo2 and PtMo2 base clusters
No full textActivation of small molecules by an amphiphilic phosphinito bridged Pt(I)-Pt(I) complex
No full textThe complex [(PHCy2)Pt(μ-PCy2){κ2P,O-μ-P(O)Cy2}Pt(PHCy2)](Pt-Pt) (1) constitutes a rare example of unsymmetrical phosphinito diplatinum species that, due to the simultaneous presence of a soft binding atom (P) linked to a hard one (O), undergoes smooth reaction with nucleophiles, electrophiles, dihydrogen and terminal alkynes. The tested nucleophiles were PHCy2, PCy3, P(S)HCy2 and CO, whereas the investigated electrophiles were several Brønsted acids as well as metal based species (AuCl, Au(PPh3)Cl, AgX, X = OTf, BF4, ClO4, Cl, (PPh3)OTf). The alkynes used in reaction with 1 were (trimethylsilyl)acetylene and phenylacetylene. In all cases the skeletal framework was preserved and in one case (reaction with diluted HF) dimerization led to a tetranuclear species
Reactions of a phosphinito bridged diplatinum(I) complex with coinage metal electrophiles
No full textWe have recently described the synthesis of the complex
[(PHCy2)Pt1(m-PCy2){k2P,O-m-P(O)Cy2}Pt2(PHCy2)] (Pt-Pt)
(1), the first unsymmetrical phosphinito bridged Pt(I) species.[1]
The phosphinito bridge differentiates the charge distributions on
the two platinum atoms as confirmed by NMR spectroscopy
(dPt(1) = -4798 ppm, dPt(2) = -5207 ppm) and DFT studies. Complex
1 shows a rich chemistry as it reacts with nucleophiles [PHCy2,
PCy3, P(S)HCy2],[2] protic species HX [P(OH)Cy2, PhSH, HF,
HCl, HBr, HI, HBF4],[3, 4] and small molecules such as H2.[5]
Recently, we started investigations on the reactivity of complex 1
towards Au and Ag based electrophiles.
In this communication, it will be shown that, differently
from the isolobal H+ (which attacks the phosphinito oxygen and
migrates onto the Pt-Pt bond),3 the [Ag(PPh3)]+ electrophile
attacks complex 1 selectively to the Pt2-mP bond to afford the
cationic cluster [(PHCy2)Pt1(m-PCy2){k2P,O-m-P(O)Cy2}Pt2{m-
-Ag(PPh3)}(PHCy2)]+ (Pt–Pt) (2+) in which the [Ag(PPh3)]+
moiety bridges the mP-Pt2 bond. Analogous reactivity is observed
also when phosphane free electrophiles such as AgOTf, AgBF4,
AgClO4 and AgCl are used. Moreover, the reactivity of 1 towards
Au(I) electrophiles such as AuCl and [Au(PPh3)Cl] was dependent
on the reagent and on the experimental conditions.
references:
1. Gallo, V.; Latronico, M.; Mastrorilli, P.; Nobile, C. F.;
Suranna, G. P.; Ciccarella, G.; Englert, U.; Eur. J. Inorg.
Chem., 2005, 4607–4616.
2. Gallo, V.; Latronico, M.; Mastrorilli, P.; Nobile, C. F.;
Polini, F.; Re, N.; Englert, U.; Inorg. Chem., 2008, 47,
4785–4795.
3. Latronico, M.; Polini, F.; Gallo, V.; Mastrorilli, P;
Calmuschi-Cula B.; Englert, U.; Re, N.; Repo T.,
Raisanen M.; Inorg. Chem., 2008, 47, 9979-9796.
4. M. Latronico, P. Mastrorilli, V. Gallo, M.M.Dell’Anna,
F. Creati, N. Re, U. Englert, Inorg. Chem. 2011, 50,
3539–3558
5. Mastrorilli P., Latronico M., Gallo V., Polini F., Re N.,
Marrone A., Gobetto R., Ellena S.. J. Am. Chem. Soc.
2010, 132, 4752–476
Role of the Pt-O fragment in the reactivity of a phosphinito bridged diplatinum(I) complex
No full textC-C bond forming reactions in ionic liquid: the effect of the impurities on catalytic performance
No full textMetodo e dispositivo di determinazione della propensione alla conservazione di uva da tavola
No full textSynthesis of Heterodimetallic Complexes by Reaction of a Terminal Phosphido Pt Complex with Metal Based Nucleophiles and Electrophiles
No full textThe complex trans-[PtCl(PCy2)(PHCy2)2] (1) possesses a terminal
phosphanido group (PCy2) and a chloride ligand,
which render it a good candidate for the synthesis of phosphanido-
bridged heterodimetallic species (PHCy2)2Pt(μ-
PCy2)M–L by reaction either with carbonyl metalates, as
metal-based nucleophiles, or with metal-based electrophiles.
The heterodinuclear complexes [(PHCy2)2Pt(μ-PCy2)Co-
(CO)3](Pt–Co) (2), [(PHCy2)2Pt(μ-PCy2)Mo(CO)2Cp](Pt–Mo)
(3), and [(PHCy2)2Pt(μ-PCy2)W(CO)2Cp](Pt–W) (4) are obtained
by reaction of 1 with the carbonyl metalates Na[Co-
(CO)4], Na[Mo(CO)3Cp] and Na[W(CO)3Cp], respectively.
Although 2 is reluctant to react with carbon monoxide, 3 and
4 are promptly carbonylated under ambient conditions to afford
mixtures of the cis and trans isomers of [(PHCy2)(CO)-
Pt(μ-PCy2)M(CO)2Cp] (M = Mo or W), which interconvert
through dissociation/reassociation of the CO ligand coordinated
to the Pt centre. The reaction of 1 with AuCl(PPh3)
leads to the formation of the trinuclear Pt2Au complexes cisand
trans-[{Cl(PHCy2)2Pt(μ-PCy2)}2Au]Cl (cis- and trans-
[8]Cl), in which a Au atom bridges two molecules of 1
through the originally terminal phosphanide ligands
The role of the Pt-M bond strength in the reactivity of DPPA-like Pt(II) complexes towards metal carbonyl anions
No full text- …
