TY - JOUR
T1 - (Ferrocenylpyrazolyl)palladium(II) complexes
T2 - Syntheses, characterization and rearrangement in solution
AU - Obuah, Collins
AU - Darkwa, James
N1 - Publisher Copyright:
© 2015 Elsevier B.V. All rights reserved.
PY - 2016/1/15
Y1 - 2016/1/15
N2 - Reactions of L1-L6 (3-ferrocenylpyrazolyle (L1), 3-ferrocenyl-5-methylpyrazolyle (L2) 3-ferrocenylpyrazolyl-methylenepyridine (L3) and 3-ferrocenyl-5-methylpyrazolylmethylene-pyridine (L4), 3-ferrocenylpyrazolylethylamine (L5) and 3-ferrocenyl-5-methylpyrazolylethyl-amine (L6)) with [PdCl(Me) (cod)] formed the mononuclear complexes [PdCl(Me) (κ1-L1)2] (1), [PdCl(Me) (κ1-L2)2] (2), [PdCl(Me) (κ2-L3)] (3), [PdCl(Me) (κ2-L4)] (4), [PdCl(Me) (κ2-L5)] (5) and [PdCl(Me) (κ2-L6)] (6). Reactions of 1-6 with the halide abstractor, Na[BAr4], (Ar = 3,5-(CF3)2C6H3), led to the formation of the salts, [PdMe(NCMe) (κ1-L1)2][BAr4] (7), [PdMe(NCMe) (κ1-L2)2][BAr4] (8), [PdMe(NCMe) (κ2-L3)][BAr4] (9), [PdMe(NCMe) (κ2-L4)][BAr4] (10), [PdMe(NCMe) (κ2-L5)][BAr4] (11), [PdMe(NCMe) (κ2-L6)][BAr4] (12) respectively. However, when 3 or 4 was reacted with of Na[BAr4] and a slight excess of methyl acrylate, the products were surprisingly the bis(ligand)palladium complexes [Pd(κ2-L3)2][BAr4]2 (13) and [Pd(κ2-L4)2][BAr4]2 (14) instead of the expected acylpalladium chelate complexes ([(κ2-L)Pd{(CH2)2C(O)OMe}][BAr4]). Complexes 1-6, activated with Na[BAr4], and pre-activated complexes 7-12 at 10 bar of ethylene and 30 bar of carbon monoxide produced polyketones, albeit with low activity (ca. 1.00 g.mmol-1Pd.h-1); with the active catalysts rearranging to mainly bis(pyrazolyl)palladium complexes similar to 13 and 14.
AB - Reactions of L1-L6 (3-ferrocenylpyrazolyle (L1), 3-ferrocenyl-5-methylpyrazolyle (L2) 3-ferrocenylpyrazolyl-methylenepyridine (L3) and 3-ferrocenyl-5-methylpyrazolylmethylene-pyridine (L4), 3-ferrocenylpyrazolylethylamine (L5) and 3-ferrocenyl-5-methylpyrazolylethyl-amine (L6)) with [PdCl(Me) (cod)] formed the mononuclear complexes [PdCl(Me) (κ1-L1)2] (1), [PdCl(Me) (κ1-L2)2] (2), [PdCl(Me) (κ2-L3)] (3), [PdCl(Me) (κ2-L4)] (4), [PdCl(Me) (κ2-L5)] (5) and [PdCl(Me) (κ2-L6)] (6). Reactions of 1-6 with the halide abstractor, Na[BAr4], (Ar = 3,5-(CF3)2C6H3), led to the formation of the salts, [PdMe(NCMe) (κ1-L1)2][BAr4] (7), [PdMe(NCMe) (κ1-L2)2][BAr4] (8), [PdMe(NCMe) (κ2-L3)][BAr4] (9), [PdMe(NCMe) (κ2-L4)][BAr4] (10), [PdMe(NCMe) (κ2-L5)][BAr4] (11), [PdMe(NCMe) (κ2-L6)][BAr4] (12) respectively. However, when 3 or 4 was reacted with of Na[BAr4] and a slight excess of methyl acrylate, the products were surprisingly the bis(ligand)palladium complexes [Pd(κ2-L3)2][BAr4]2 (13) and [Pd(κ2-L4)2][BAr4]2 (14) instead of the expected acylpalladium chelate complexes ([(κ2-L)Pd{(CH2)2C(O)OMe}][BAr4]). Complexes 1-6, activated with Na[BAr4], and pre-activated complexes 7-12 at 10 bar of ethylene and 30 bar of carbon monoxide produced polyketones, albeit with low activity (ca. 1.00 g.mmol-1Pd.h-1); with the active catalysts rearranging to mainly bis(pyrazolyl)palladium complexes similar to 13 and 14.
KW - Carbon monoxide
KW - Copolymerization
KW - Ethylene
KW - Ferrocenylprazolyl
KW - Palladium complexes
UR - http://www.scopus.com/inward/record.url?scp=84949845088&partnerID=8YFLogxK
U2 - 10.1016/j.jorganchem.2015.11.003
DO - 10.1016/j.jorganchem.2015.11.003
M3 - Article
AN - SCOPUS:84949845088
SN - 0022-328X
VL - 802
SP - 39
EP - 48
JO - Journal of Organometallic Chemistry
JF - Journal of Organometallic Chemistry
ER -