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.
| 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 | |
| Publication status | Published - Dec 19 2007 |
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ASJC Scopus subject areas
- Chemistry(all)
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Metal-dependent reactivity differences for transients formed by flash photolysis of (PNP)M(CO), M = Co and Rh. / Rimmer, R. Dale; Grills, David C.; Fan, Hongjun; Ford, Peter C.; Caulton, Kenneth G.
In: Journal of the American Chemical Society, Vol. 129, No. 50, 19.12.2007, p. 15430-15431.Research output: Contribution to journal › Article
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TY - JOUR
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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U2 - 10.1021/ja076357l
DO - 10.1021/ja076357l
M3 - Article
VL - 129
SP - 15430
EP - 15431
JO - Journal of the American Chemical Society
JF - Journal of the American Chemical Society
SN - 0002-7863
IS - 50
ER -