Metal-Dependent Reactivity Differences for Transients Formed By Flash Photolysis of (PNP)M(CO), M = Co and Rh.

Metal-Dependent Reactivity Differences for Transients Formed By Flash Photolysis of (PNP)M(CO), M = Co and Rh. Research Abstract Details 

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Metal-Dependent Reactivity Differences for Transients Formed By Flash Photolysis of (PNP)M(CO), M = Co and Rh. Abstract Text:

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

Spin triplet (PNP)Co adds one CO according to a rate law first-order in each reagent with k = 9.3 x 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 [eta4-tBu2PCH2SiMe2NSiMe2CH2PtBu(CMe2CH2)]RhH, and this adds CO with a second-order rate constant of 6 x 106 M-1 s-1. The resulting monocarbonyl then slowly (k = 3 x 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.

Metal-Dependent Reactivity Differences for Transients Formed By Flash Photolysis of (PNP)M(CO), M = Co and Rh. Publishing Authors By Initials

RD Rimmer,DC Grills,H Fan,PC Ford,KG Caulton,RD Rimmer,DC Grills,H Fan,PC Ford,KG Caulton,RD Rimmer,DC Grills,H Fan,PC Ford,KG Caulton,

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Metal-Dependent Reactivity Differences for Transients Formed By Flash Photolysis of (PNP)M(CO), M = Co and Rh. Journal Published:

PUBLICATION TYPE: Journal Article

Journal: Journal of the American Chemical Society

VOLUME: 129

Page Numbers: 15430-1

Journal Abbreviation: J. Am. Chem. Soc.

ISSN: 1520-5126

DAY: 21

MONTH: 11

YEAR: 2007

Metal-Dependent Reactivity Differences for Transients Formed By Flash Photolysis of (PNP)M(CO), M = Co and Rh. Information

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LANGUAGE: eng

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AFFILIATION: Departments of Chemistry, University of California, Santa Barbara, California 93106, Brookhaven National Laboratory, Upton, New York 11973, and Indiana University, Bloomington, Indiana 47405.

Country: United States

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