Thermal Decomposition of Di(cycloalkyl)bis(triethylphosphine)platinum(II) Complexes

Ralph G. Nuzzo; Thomas J. McCarthy; George M. Whitesides

doi:10.1021/ja00402a026

Thermal Decomposition of Di(cycloalkyl)bis(triethylphosphine)platinum(II) Complexes

Ralph G. Nuzzo, Thomas J. McCarthy, George M. Whitesides

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Abstract

The thermal decompositions of three di(cycloalkyl)bis(triethylphosphine)platinum(II) complexes [cycloalkyl = cyclopropyl (L₂Pt(c-C₃)₂), cyclobutyl (L₂Pt(c-C₄)₂), cyclopentyl (L₂Pt(c-C₅)₂)] have been examined. The mechanisms of decomposition of L₂Pt(c-C₄)₂ and L₂Pt(c-C₅)₂ are similar to those established in greater detail for diethylbis(triethylphosphine)platinum(II). The individual steps in solutions containing low concentrations of free triethylphosphine are dissociation of triethylphosphine and creation of a vacant coordination site, β-hydride elimination, and reductive elimination of cycloalkane (Scheme I); either the first or the third of these steps may be rate limiting. At high [L], another path having two triethylphosphines on platinum in the rate-determining transition state is important. Both enthalpic and entropic terms are important in determining which mechanism for decomposition is followed. Thermal decomposition of L₂Pt(c-C₃)₂ is complex and is not presently understood: isomerization of cis-L₂Pt(c-C₃)₂ to trans-L₂Pt(c-C₃)₂, hydrogen transfer from L to the cyclopropyl group, and opening of the cyclopropyl ring are all competitive processes.

Original language	English (US)
Pages (from-to)	3404-3410
Number of pages	7
Journal	Journal of the American Chemical Society
Volume	103
Issue number	12
DOIs	https://doi.org/10.1021/ja00402a026
State	Published - Jun 1981
Externally published	Yes

ASJC Scopus subject areas

Catalysis
General Chemistry
Biochemistry
Colloid and Surface Chemistry

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10.1021/ja00402a026

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@article{786a5a7fb9fa465f94c30da554ce1b2b,

title = "Thermal Decomposition of Di(cycloalkyl)bis(triethylphosphine)platinum(II) Complexes",

abstract = "The thermal decompositions of three di(cycloalkyl)bis(triethylphosphine)platinum(II) complexes [cycloalkyl = cyclopropyl (L2Pt(c-C3)2), cyclobutyl (L2Pt(c-C4)2), cyclopentyl (L2Pt(c-C5)2)] have been examined. The mechanisms of decomposition of L2Pt(c-C4)2 and L2Pt(c-C5)2 are similar to those established in greater detail for diethylbis(triethylphosphine)platinum(II). The individual steps in solutions containing low concentrations of free triethylphosphine are dissociation of triethylphosphine and creation of a vacant coordination site, β-hydride elimination, and reductive elimination of cycloalkane (Scheme I); either the first or the third of these steps may be rate limiting. At high [L], another path having two triethylphosphines on platinum in the rate-determining transition state is important. Both enthalpic and entropic terms are important in determining which mechanism for decomposition is followed. Thermal decomposition of L2Pt(c-C3)2 is complex and is not presently understood: isomerization of cis-L2Pt(c-C3)2 to trans-L2Pt(c-C3)2, hydrogen transfer from L to the cyclopropyl group, and opening of the cyclopropyl ring are all competitive processes.",

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year = "1981",

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AU - Nuzzo, Ralph G.

AU - McCarthy, Thomas J.

AU - Whitesides, George M.

PY - 1981/6

Y1 - 1981/6

N2 - The thermal decompositions of three di(cycloalkyl)bis(triethylphosphine)platinum(II) complexes [cycloalkyl = cyclopropyl (L2Pt(c-C3)2), cyclobutyl (L2Pt(c-C4)2), cyclopentyl (L2Pt(c-C5)2)] have been examined. The mechanisms of decomposition of L2Pt(c-C4)2 and L2Pt(c-C5)2 are similar to those established in greater detail for diethylbis(triethylphosphine)platinum(II). The individual steps in solutions containing low concentrations of free triethylphosphine are dissociation of triethylphosphine and creation of a vacant coordination site, β-hydride elimination, and reductive elimination of cycloalkane (Scheme I); either the first or the third of these steps may be rate limiting. At high [L], another path having two triethylphosphines on platinum in the rate-determining transition state is important. Both enthalpic and entropic terms are important in determining which mechanism for decomposition is followed. Thermal decomposition of L2Pt(c-C3)2 is complex and is not presently understood: isomerization of cis-L2Pt(c-C3)2 to trans-L2Pt(c-C3)2, hydrogen transfer from L to the cyclopropyl group, and opening of the cyclopropyl ring are all competitive processes.

AB - The thermal decompositions of three di(cycloalkyl)bis(triethylphosphine)platinum(II) complexes [cycloalkyl = cyclopropyl (L2Pt(c-C3)2), cyclobutyl (L2Pt(c-C4)2), cyclopentyl (L2Pt(c-C5)2)] have been examined. The mechanisms of decomposition of L2Pt(c-C4)2 and L2Pt(c-C5)2 are similar to those established in greater detail for diethylbis(triethylphosphine)platinum(II). The individual steps in solutions containing low concentrations of free triethylphosphine are dissociation of triethylphosphine and creation of a vacant coordination site, β-hydride elimination, and reductive elimination of cycloalkane (Scheme I); either the first or the third of these steps may be rate limiting. At high [L], another path having two triethylphosphines on platinum in the rate-determining transition state is important. Both enthalpic and entropic terms are important in determining which mechanism for decomposition is followed. Thermal decomposition of L2Pt(c-C3)2 is complex and is not presently understood: isomerization of cis-L2Pt(c-C3)2 to trans-L2Pt(c-C3)2, hydrogen transfer from L to the cyclopropyl group, and opening of the cyclopropyl ring are all competitive processes.

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Thermal Decomposition of Di(cycloalkyl)bis(triethylphosphine)platinum(II) Complexes

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