61771-08-2Relevant academic research and scientific papers
Synthesis of a novel volatile platinum complex for use in CVD and a study of the mechanism of its thermal decomposition in solution
Tagge, Christopher D.,Simpson, Robert D.,Bergman, Robert G.,Hosteller, Michael J.,Girolami, Gregory S.,Nuzzo, Ralph G.
, p. 2634 - 2643 (1996)
The synthesis, characterization, chemical vapor deposition, and mechanistic investigation of the thermal decomposition in aromatic solvents of cis-bis(η2,η1-pent-4-en-1-yl)platinum (1) are described. Complex 1 has a unique chelated structure, giving rise to enhanced volatility, and has proved useful for the chemical vapor deposition of thin platinum films under mild conditions. Films deposited on a glass slide in a hot walled glass tube at 175°C have an elemental composition of 82% Pt and 18% C. Kinetic, deuterium labeling and chemical trapping experiments indicate that the decomposition of 1 in aromatic solvents proceeds by reversible β-hydride elimination followed by reversible dissociation of 1,4-pentadiene to give a 3-coordinate platinum hydride intermediate (9). Reductive elimination of 1-pentene from 9 deposits metallic platinum. The rate of decomposition exhibits a significant β-deuterium isotope effect of kH/kD=3.8±0.3. Added olefins are rapidly isomerized during the decomposition of 1: trapping experiments with diphenylacetylene indicate that intermediate 9 is the highly active catalyst that is responsible for the alkene isomerization. The synthesis, characterization, chemical vapor deposition, and mechanistic investigation of the thermal decomposition in aromatic solvents of cis-bis(η2,η1-pent-4-en-1-yl)platinum (1) are described. Complex 1 has a unique chelated structure, giving rise to enhanced volatility, and has proved useful for the chemical vapor deposition of thin platinum films under mild conditions. Films deposited on a glass slide in a hot walled glass tube at 175°C have an elemental composition of 82% Pt and 18% C. Kinetic, deuterium labeling, and chemical trapping experiments indicate that the decomposition of 1 in aromatic solvents proceeds by reversible β-hydride elimination followed by reversible dissociation of 1,4-pentadiene to give a 3-coordinate platinum hydride intermediate (9). Reductive elimination of 1-pentene from 9 deposits metallic platinum. The rate of decomposition exhibits a significant β-deuterium isotope effect of k(H)/k(D) = 3.8 ± 0.3. Added olefins are rapidly isomerized during the decomposition of 1; trapping experiments with diphenylacetylene indicate that intermediate 9 is the highly active catalyst that is responsible for the alkene isomerization.
Two alternative, convenient routes to bis(diphenylacetylene)platinum(0)
Huber, Christian,Kokil, Akshay,Caseri, Walter R.,Weder, Christoph
, p. 3817 - 3818 (2002)
Two new synthetic routes are presented that allow the convenient preparation and isolation of bis-(diphenylacetylene)platinum(0) under ambient conditions. The first procedure is based on a ligand exchange reaction between Ph-C≡C-Ph and tris(styrene)platinum(0). The second framework relies on the reduction of cis-[PtCl2(PhCH=CH2)2] with triphenylsilane in the presence of diphenylacetylene.
Platinum(II) Di-ω-alkenyl Complexes as slow-Release Precatalysts for Heat-Triggered Olefin Hydrosilylation
Girolami, Gregory S.,Liu, Sumeng
supporting information, p. 17492 - 17509 (2021/11/04)
We describe the synthesis, characterization, and catalytic hydrosilylation activity of platinum(II) di-ω-alkenyl compounds of stoichiometry PtR2, where R = CH2SiMe2(vinyl) (1) or CH2SiMe2(allyl) (2), and their adducts with 1,5-cyclooctadiene (COD), dibenzo[a,e]cyclooctatetraene (DBCOT), and norbornadiene (NBD), which can be considered as slow-release sources of the reactive compounds 1 and 2. At loadings of 0.5 × 10-6-5 × 10-6 mol %, 1-COD is an active hydrosilylation catalyst that exhibits heat-triggered latency: no hydrosilylation activity occurs toward many olefin substrates even after several hours at 20 °C, but turnover numbers as high as 200000 are seen after 4 h at 50 °C, with excellent selectivity for formation of the anti-Markovnikov product. Activation of the PtII precatalyst occurs via three steps: slow dissociation of COD from 1-COD to form 1, rapid reaction of 1 with silane, and elimination of both ω-alkenyl ligands to form Pt0 species. The latent catalytic behavior, the high turnover number, and the high anti-Markovnikov selectivity are a result of the slow release of 1 from 1-COD at room temperature, so that the concentration of Pt0 during the initial stages of the catalysis is negligible. As a result, formation of colloidal Pt, which is known to cause side reactions, is minimized, and the amounts of side products are very small and comparable to those seen for platinum(0) carbene catalysts. The latent reaction kinetics and high turnover numbers seen for 1-COD after thermal triggering make this compound a potentially useful precatalyst for injection molding or solvent-free hydrosilylation applications.
High charge carrier mobility in conjugated organometallic polymer networks
Kokil, Akshay,Shiyanovskaya, Irina,Singer, Kenneth D.,Weder, Christoph
, p. 9978 - 9979 (2007/10/03)
The improvement of charge transport in conjugated polymers is a focal point of current research. It is shown here that the carrier mobility can be substantially increased through the introduction of conjugated cross-links between the conjugated chains. Novel organometallic polymer networks based on a poly(p-phenylene ethynylene) (PPE) derivative and Pt0 were synthesized by ligand-exchange reactions between the linear PPE and a low-molecular Pt complex. Time-of-flight measurements revealed ambipolar charge carrier mobilities of up to 1.6 × 10-2 cm2 V-1 s-1 for these materials, which are an order of magnitude higher than those of the neat polymer and represent the highest mobilities yet observed in disordered conjugated polymers. Copyright
A convenient and novel route to bis(η-alkyne)platinum(0) and other platinum(0) complexes from Speier's hydrosilylation catalyst H2[PtCl6]·xH2O. X-ray structure of [Pt{(η-CH2=CHSiMe2)2O}(P-t-Bu3)]
Chandra, Grish,Lo, Peter Y.,Hitchcock, Peter B.,Lappert, Michael F.
, p. 191 - 192 (2008/10/08)
Evidence that the hydrosilylation catalyst, obtained by refluxing H2[PtCl6]·xH2O in (Me2ViSi)2O (solution A), is a Pt(0) species comprises (i) the isolation and X-ray characterization of [Rt{(η-CH2CHMe2Si)2O}(P-t-Bu3)], after addition of P-t-Bu3 to A, (ii) the convenient high-yield synthesis of various other Pt(0) complexes from A, and (iii) CV, GC/MS, and 195Pt NMR data.
