Cobalt Complexes Containing Pendant Amines in the Second Coordination Sphere as Electrocatalysts for H2 Production

Autor:	W. Scott Kassel, Daniel L. DuBois, Ming Fang, William G. Dougherty, Tianbiao Liu, R. Morris Bullock, Eric S. Wiedner
Rok vydání:	2014
Předmět:	Coordination sphere Chemistry Organic Chemistry Inorganic chemistry Substituent chemistry.chemical_element Protonation Crystal structure Electrochemistry Inorganic Chemistry Crystallography chemistry.chemical_compound Paramagnetism Polar effect Physical and Theoretical Chemistry Cobalt
Zdroj:	Organometallics. 33:5820-5833
ISSN:	1520-6041 0276-7333
DOI:	10.1021/om5004607
Popis:	A series of heteroleptic 17e cobalt complexes, [CpCoII(PtBu2NPh2)](BF4), [CpC6F5CoII(PtBu2NPh2)](BF4), and [CpC5F4NCoII(PtBu2NPh2)](BF4) (where PtBu2NPh2 = 1,5-diphenyl-3,7-di-tert-butyl-1,5-diaza-3,7-diphosphacyclooctane, CpC6F5 = C5H4(C6F5), and CpC5F4N = C5H4(C5F4N)) were synthesized, and the structures of all three were determined by X-ray crystallography. Electrochemical studies showed that the CoIII/II couple of [CpC5F4NCoII(PtBu2NPh2)]+ appears 250 mV positive of the CoIII/II couple of [CpCoII(PtBu2NPh2)]+ as a result of the strongly electron withdrawing perfluoropyridyl substituent on the Cp ring. Reduction of these paramagnetic CoII complexes by KC8 led to the diamagnetic 18e complexes CpCoI(PtBu2NPh2), CpC6F5CoI(PtBu2NPh2), and CpC5F4NCoI(PtBu2NPh2), which were also characterized by crystallography. Protonation of these neutral CoI complexes led to the CoIII hydrides [CpCoIII(PtBu2NPh2)H](BF4), [CpC6F5CoIII(PtBu2NPh2)H](BF4), and [CpC5F4NCoIII(PtBu2NPh2)H](BF4), and crystal structures of each of...
Databáze:	OpenAIRE
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