Synthesis of a Novel Volatile Platinum Complex for Use in CVD and a Study of the Mechanism of Its Thermal Decomposition in Solution

Abstract

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.

Transition metal-alkenyl complexes [M–(CH2)nCHCH2, n≥2]: Synthesis, structure, reactivity and applications

“…In a similar way, Benn et al [38] have synthesized the bis(alkenyl) complexes L 2 Pt{(CH 2 ) 2 CH CH 2 } 2 (where L 2 = dmpe, dcpe, dppe). In contrast, Tagge et al have shown that reacting Pt(COD)Cl 2 with pent-4-en-1-ylmagnesium bromide gives cis-bis( 1 , 2 -pent-4-en-1-yl)platinum (23), a complex in which the alkenyl ligand is bound to the metal in a 1 , 2 -fashion [37]. The complex Pt{(CH 2 ) 3 CH CH 2 } 2 (23) is air and moisture stable, but thermally sensitive in the solid state, decomposing within 2 weeks at room temperature.…”

“…While there are a number of reports on monoalkenyl complexes prepared using the various synthetic methods described above, the known bis(alkenyl) complexes are limited to platinum [37,38], molybdenum [28,29] and zirconium [36], and have been prepared exclusively by reaction of a metal halide with a Grignard reagent. No other methods are known for the synthesis of alkenyl complexes of these metals (Scheme 7).…”

“…Tagge et al [37] reported the thermal decomposition studies on cis-bis( 1 , 2 -pent-4-ene-1-yl)platinum(II) (23) as shown in Eq.…”

MOCVD of Platinum Films from (CH3)3CH3CpPt and Pt(acac)2: Nanostructure, Conformality, and Electrical Resistivity

“…[21] However, many of these Pt complexes are not commercially available, and the development of a Pt-MOCVD process for commercial-scale production is primarily restricted by the low volatility and thermal stability of solid precursors. In addition, when Pt was deposited on BST using a fluorine-containing precursor, a significant amount of fluorine contamination was observed at the interface of Pt and BST.…”

CVD of Pt(C5H9)2 to Synthesize Highly Dispersed Pt/SBA‐15 Catalysts for Hydrogenation of Chloronitrobenzene

“…Compared to many other preparation methods, MOCVD is a reproducible and controllable method of producing metal ultra‐thin films or nanoparticles, tubes, or wires. This method is widely used due to its simple experimental set‐up, convenient operation, relatively low temperature conditions, and uniform deposition quality.…”