Reactions of [PdCl2(NCMe)2] with the ferrocenylpyrazolyl compounds: 3-ferrocenyl-1H-pyrazole-5-carboxylate (L1), ethyl-1-(2-bromoethyl)-3-ferrocenyl-1H-pyrazole-5-carboxylate (L2a), ethyl-1-(2-bromoethyl)-5-ferrocenyl-1H-pyrazole-3-carboxylate (L2b), 3-ferrocenylpyrazolyl-methylenepyridine (L3) and 3-ferrocenyl-5-methylpyrazolyl-methylenepyridine (L4) at room temperature afforded [PdCl2(L1)] (1), [PdCl2(L2a)] (2a), [PdCl2(L2b)] (2b), [PdCl2(L3)] (3) and [PdCl2(L4)] (4) respectively. Compounds L1-L4 and their palladium complexes were obtained in moderate to high (50-90%) yield and characterized by NMR spectroscopy, elemental analysis, and in selected cases by single crystal X-ray crystallography. Complexes 1-4 were used as pre-catalysts for the reactions of 1-heptene and 1-octene with EtAlCl2 as a co-catalyst. The activities of 1, 2a and 3b were relatively low (10 083-18 250 g molPd(-1) h(-1)) with 1-heptene being a better monomer for these complexes. However, pre-catalysts 3 and 4 showed moderate activities (123 000-448 000 g molPd(-1) h(-1)) 1-octene being the better monomer. The polyolefins obtained were characterized by both (1)H and (13)C{(1)H} NMR to be highly branched polyolefins with degree of branching up to 270 branches per 1000 carbon atoms. However, low molecular weights between 888 and 1198 were recorded with narrow PDI between 1.02 and 1.44.
A detailed description of the procedures utilized in the non-routine X-ray single-crystal structural determination and refinement of a pseudo-merohedrally twinned crystal of an Fe/Ni organometallic complex is presented. It illustrates to the practitioners of crystallography how to properly handle such cases and describes the logic and concrete steps necessary to account for the twinning, pseudo-symmetry and atomic positional disorder.
Dedicated to Prof. Helgard G. Raubenheimer on the occasion of his 65 th birthdayfriend and colleague over many decadesReactions of (η 5 -RC 5 H 4 )Fe(CO) 2 I (R = H, Me) complexes with phosphine ligands PR 3 (R = Ph, m-Tol, p-C 6 H 4 OMe, p-C 6 H 4 Cl, p-C 6 H 4 F) have been performed under solvent-free conditions in the melt phase and generally yielded the ionic products [(η 5 -RC 5 H 4 )Fe(CO) 2 PR 3 ]I rather than the CO substituted products (η 5 -RC 5 H 4 )Fe(CO)(PR 3 )I. The complexes have been characterised by IR, NMR and MS techniques. By contrast, the same reactions studied in benzene solution have yielded mainly the CO substitution products. Factors that affect the solvent-free reaction include variation in R and R , reaction temperature and the addition of [CpFe(CO) 2 ] 2 as a catalyst. The mechanism of the reaction for the formation of the ionic complex is proposed to go via a 19 electron intermediate. This is in contrast to the reaction in bezene that occurs via a 17 electron intermediate, clearly indicating the role of the melt phase in the reaction.
Reaction between solid (C5H5)Fe(CO)2CH3 and a range of solid phosphine ligands, L (L = PPh3, P(m-CH3C6H4)3, P(p-CH3C6H4)3, P(p-FC6H4)3, P(p-ClC6H4)3, PCy3) occurred in the absence of solvent in the melt phase to give the migratory-insertion products, (C5H5)Fe(CO)(COCH3)(L). The reaction was more rapid with small electron withdrawing ligands. Insertion reaction between (RC5H4)Fe(CO)2R' (R = H, CH3; R' = CH3, CH2Ph) and gaseous ligands such as SO2 and CO were also studied. The insertion of SO2 occurred readily for all the substrates investigated, but CO insertion did not occur (< 1 %) using the solventless reaction condition.
The title compound, [Ru(C5H5)I(CO)2], has a three-legged piano-stool geometry with a distorted pseudo-octahedral structure. The cyclopentadienyl ring is disordered over two sets of positions.
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