Metal-dependent reactivity differences for transients formed by flash photolysis of (PNP)M(CO), M = Co and Rh

R. Dale Rimmer; David C. Grills; Hongjun Fan; Peter C. Ford; Kenneth G. Caulton

doi:10.1021/ja076357l

Metal-dependent reactivity differences for transients formed by flash photolysis of (PNP)M(CO), M = Co and Rh

R. Dale Rimmer, David C. Grills, Hongjun Fan, Peter C. Ford, Kenneth G. Caulton

Brookhaven National Laboratory

Research output: Contribution to journal › Article › peer-review

9 Citations (Scopus)

Abstract

Spin triplet (PNP)Co adds one CO according to a rate law first-order in each reagent with k = 9.3 × 10⁵ M^-1 s^-1. In contrast, the transient produced by photodissociation of CO from (PNP)Rh(CO) forms, within 10 ns, the Rh(III) species [η^4-tBu₂PCH₂SiMe₂NSiMe₂CH₂P^tBu(CMe₂CH₂)]RhH, and this adds CO with a second-order rate constant of 6 × 10⁶ M^-1 s^-1. The resulting monocarbonyl then slowly (k = 3 × 10¹ s^-1) reductively eliminates H and C(sp³) to re-form (PNP)Rh(CO). The former two rate constants support the idea that a spin crossing between triplet (PNP)Co and singlet (PNP)Co(CO) causes a rate suppression.

Original language	English
Pages (from-to)	15430-15431
Number of pages	2
Journal	Journal of the American Chemical Society
Volume	129
Issue number	50
DOIs	https://doi.org/10.1021/ja076357l
Publication status	Published - Dec 19 2007

ASJC Scopus subject areas

Catalysis
Chemistry(all)
Biochemistry
Colloid and Surface Chemistry

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title = "Metal-dependent reactivity differences for transients formed by flash photolysis of (PNP)M(CO), M = Co and Rh",

abstract = "Spin triplet (PNP)Co adds one CO according to a rate law first-order in each reagent with k = 9.3 × 105 M-1 s-1. In contrast, the transient produced by photodissociation of CO from (PNP)Rh(CO) forms, within 10 ns, the Rh(III) species [η4-tBu2PCH2SiMe2NSiMe2CH2PtBu(CMe2CH2)]RhH, and this adds CO with a second-order rate constant of 6 × 106 M-1 s-1. The resulting monocarbonyl then slowly (k = 3 × 101 s-1) reductively eliminates H and C(sp3) to re-form (PNP)Rh(CO). The former two rate constants support the idea that a spin crossing between triplet (PNP)Co and singlet (PNP)Co(CO) causes a rate suppression.",

author = "Rimmer, {R. Dale} and Grills, {David C.} and Hongjun Fan and Ford, {Peter C.} and Caulton, {Kenneth G.}",

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T1 - Metal-dependent reactivity differences for transients formed by flash photolysis of (PNP)M(CO), M = Co and Rh

AU - Rimmer, R. Dale

AU - Grills, David C.

AU - Fan, Hongjun

AU - Ford, Peter C.

AU - Caulton, Kenneth G.

PY - 2007/12/19

Y1 - 2007/12/19

N2 - Spin triplet (PNP)Co adds one CO according to a rate law first-order in each reagent with k = 9.3 × 105 M-1 s-1. In contrast, the transient produced by photodissociation of CO from (PNP)Rh(CO) forms, within 10 ns, the Rh(III) species [η4-tBu2PCH2SiMe2NSiMe2CH2PtBu(CMe2CH2)]RhH, and this adds CO with a second-order rate constant of 6 × 106 M-1 s-1. The resulting monocarbonyl then slowly (k = 3 × 101 s-1) reductively eliminates H and C(sp3) to re-form (PNP)Rh(CO). The former two rate constants support the idea that a spin crossing between triplet (PNP)Co and singlet (PNP)Co(CO) causes a rate suppression.

AB - Spin triplet (PNP)Co adds one CO according to a rate law first-order in each reagent with k = 9.3 × 105 M-1 s-1. In contrast, the transient produced by photodissociation of CO from (PNP)Rh(CO) forms, within 10 ns, the Rh(III) species [η4-tBu2PCH2SiMe2NSiMe2CH2PtBu(CMe2CH2)]RhH, and this adds CO with a second-order rate constant of 6 × 106 M-1 s-1. The resulting monocarbonyl then slowly (k = 3 × 101 s-1) reductively eliminates H and C(sp3) to re-form (PNP)Rh(CO). The former two rate constants support the idea that a spin crossing between triplet (PNP)Co and singlet (PNP)Co(CO) causes a rate suppression.

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