15376-99-5Relevant academic research and scientific papers
CO-Induced Reductive Elimination of P(t-Bu)2H from the Platinum(II) Dinuclear Derivative Pt2[μ-P(t-Bu)2]2(H)2[P(t-Bu) 2H]2, Affording Mononuclear Platinum(0) or Triangulo Triplatinum(I,I,II) Derivatives
Leoni, Piero,Manetti, Silvia,Pasquali, Marco,Albinati, Alberto
, p. 6045 - 6052 (1996)
Carbon monoxide (1 atm) quantitatively converts the Pt(II) dinuclear derivative Pt2[μ-P(t-Bu)2]2(H)2[P(t-Bu) 2H]2 (1) into the new PtI2PtII triangulo cluster Pt3[μ-P(t-Bu)2]3(H)(CO)2 (2). The 44e- species 2 was characterized by IR and multinuclear NMR spectroscopy and by a single-crystal X-ray diffraction study. Complex 2 is formed through the slow CO-induced reductive elimination of P(t-Bu)2H from 1, affording the intermediate mononuclear Pt(0) carbonyl derivative Pt[P(t-Bu)2H]2(CO)2 (4), which equilibrates with the carbonyl-bridged triangulo derivative Pt3[P(t-Bu)2H]3(μ-CO)3 (5); these are the main products under high pressures of CO. Two alternative mechanisms were examined for the subsequent formation of complex 2, the first being the rapid condensation of complex 4 with unreacted 1 while the second assumes 5 as the direct precursor of 2. Although the first mechanism cannot be conclusively rejected, the second seems the most appropriate, since under high pressures of CO/H2 complex 2 was shown to equilibrate with 5. In the presence of an excess of other phosphides, the carbonylation of 1 yields quantitatively the mononuclear monocarbonyl derivatives Pt(PR3)3(CO) (R3 = Ph3, Et3, t-Bu2H).
Synthesis of PtRe2 and Pt2Re2 Heterometallic Complexes from the Reaction of Dirhenium Carbonyl Compounds with Zerovalent Complexes of Platinum
Powell, John,Brewer, John C.,Gulia, Giulia,Sawyer, Jeffery F.
, p. 2503 - 2516 (2007/10/02)
The monoacetonitrile complex , obtained from the reaction of with freshly prepared iodosobenzene in acetonitrile solutions, reacts with the secondary phosphines PR2H in refluxing hexane to give the complexes (5a, R = Ph; 5b, R = Pr).Complexes 5, when heated to > 170 deg C in decalin, lose CO and are converted cleanly to (6a, R = Ph; 6b, R = Pr) while they react with to give (7a, R = Ph; 7b, R = Pr), complexes containing a triangular PtRe2 array withPt(μ-PR2)Re, Pt(μ-H)Re and Re-Re edges.Similarly, reaction of complexes 5 with > gives > 8 containing Pt(μ-CO)Re, Pt(μ-H)Re and Re(μPR2)Re edges.The trimetallic complex 8 slowly disproportionates to give 6 and 1/3 3>.The reaction of 6a (μ-PPh2) with > gives the complex > 7c in which the μ-PPh2 ligand has migrated from a ReRe edge in 6a to a PtRe edge in 7.Further reaction of 7c with a second equivalent of > yields the tetrametallic complex 2> 10 (μ-PPh2, μ-H and 2μ-CO on Pt-Re edges).Reaction of with > gives > and 2> 12 (4μ-CO on PtRe edges).The molecular structures of 7 b, 10 and 12 have been determined by single-crystal X-ray diffraction studies.Crystal data as follows: 7b, orthorombic, space group Pbca, a = 14.951(2), b = 18.330(2), c = 25.715(2) Angstroem, Z = 8, R = 0.0521 (R' = 0.0597) for 3700 data with I >= 3?(I); 10, monoclinic space group, P21/n, a = 15.215(9), b = 19.633(9), c = 19.446(8) Angstroem, β = 92.90(4) deg, Z = 4, R = 0.0950 (R' = 0.1006) for 6068 data with I >= 3?(I); and 12, triclinic (paramonoclinic) space group, P1/, a = 11.567(4), b = 15.308(6), c = 16.178(6) Angstroem, α = 89.87(3), β = 108.13(3), γ = 90.28(3) deg, Z = 2, R = 0.0659 (R' = 0.0716) for 7166 data with I >= 3?(I).
Preparation and properties of platinum ketene complexes. Facile C-C bond cleavage of coordinated ketene
Miyashita, Akira,Shitara, Hiroaki,Nohira, Hlroyuki
, p. 1463 - 1464 (2008/10/08)
η2-(C,C) ketene complexes Pt(CH2=C=O)L2 (L = PPh3 and Cl) and PtCl2(CH2=C=O) (PMe2Ph)2, which were isolated from the reaction of PtL4 with CH2Br2 and carbon monoxide in the presence of Zn or direct ligation of PtL4 with ketene, thermally decomposed to afford a variety of hydrocarbons by a novel pathway involving C-C bond cleavage of the bound ketenes and underwent reduction with H2 to yield acetaldehyde, ethanol, and hydrocarbons.
REACTIVITY OF CARBON SUBOXIDE TOWARD (PPh3)2Pt(C2H4): A CHAMELEONIC BEHAVIOUR
Pandolfo, Luciano,Morandini, Franco,Paiaro, Gastone
, p. 711 - 714 (2007/10/02)
Carbon suboxide, C3O2, reacts with (PPh3)2Pt(C2H4) showing different behaviours.If the reaction is carried out in the presence of CO2, a metallacyclopropanonic compound, (PPh3)2PtC3O2, is the sole product, whereas if CO2 is absent, η2-C,O-2C3O2 is obtained.Finally, if the reaction is carried out in boiling solvent, decarbonylation occurs, with formation of (PPh3)3PtCO as the main product.Factors determining these different behaviours are briefly discussed.
REACTIONS INVOLVING TRANSITION METALS. XIX. SOME REACTIONS OF PERFLUORONORBORNADIENE WITH LOW VALENT TRANSITION METAL COMPLEXES
Booth, Brian L.,Casey, Sylvia,Haszeldine, Robert N.
, p. 289 - 300 (2007/10/02)
Perfluoronorbornadiene reacts with the compounds to give the adducts and in which one of the double bonds is coordinated to the metal atom.The platinum complex reacts further with to give 2> having both double bonds coordinated to a Pt atom.The carbonylmetal anions -> react to form the mono-substitution products (M = Mn(CO)5, Re(CO)5, Ir(CO)2(PPh3)2, Rh(CO)2(PPh3)2, but the use of an excess of - leads to substitution of one fluorine atom on each of the double bonds.The complex having M = Mn(CO)5 reacts with to afford the derivative >, and the compound where M = Ir(CO)2(PPh3)2 undergoes an oxidative addition reaction with acetyl chloride.Oxidative coupling products have been isolated on UV irradiation of a mixture of perfluoronorbornadiene and 4-CH2=CRCH=CH2)(CO)3> (R = H, Me), and under similar conditions the reaction with Fe(CO)5 affords in very low yield.
