Papers by Mattia Giacomello
An entry from the Cambridge Structural Database, the world's repository for small molecule cr... more An entry from the Cambridge Structural Database, the world's repository for small molecule crystal structures. The entry contains experimental data from a crystal diffraction study. The deposited dataset for this entry is freely available from the CCDC and typically includes 3D coordinates, cell parameters, space group, experimental conditions and quality measures.
Organometallics, 2014
ABSTRACT The diazoalkane complexes [Ru(η5-C5H5)(N2CAr1Ar2)(PPh3)(L)]BPh4 (1-5: Ar1 = Ar2 = Ph (a)... more ABSTRACT The diazoalkane complexes [Ru(η5-C5H5)(N2CAr1Ar2)(PPh3)(L)]BPh4 (1-5: Ar1 = Ar2 = Ph (a), Ar1 = Ph and Ar2 = p-tolyl (b), Ar1Ar2 = C12H8 (c), Ar1 = Ph and Ar2 = PhCO (d); L = PPh3 (1), P(OMe)3 (2), P(OEt)3 (3), PPh(OEt)2 (4), ButNC (5)) were prepared by allowing the chloro compounds RuCl(η5-C5H5)(PPh3)(L) to react with the diazoalkanes Ar1Ar2CN2 in ethanol. Treatment of complexes 1-5 with ethylene (CH2═CH2) under mild conditions (1 atm, room temperature) led not only to the η2-ethylene complexes [Ru(η5-C5H5)(η2-CH2═CH2)(PPh3)(L)]BPh4 (10-14) but also to dipolar (3 + 2) cycloaddition, affording the 4,5-dihydro-3H-pyrazole derivatives [Ru(η5-C5H5){η1-N═NC(Ar1Ar2)CH2CH2}(PPh3)(L)]BPh4 (6-9). Acrylonitrile (CH2═C(H)CN) reacted with diazoalkane complexes 2 and 3 to give the 1H-pyrazoline derivatives [Ru(η5-C5H5){η1-N═C(CN)CH2C(Ar1Ar2)NH}(PPh3)(L)]BPh4 (19, 20). However, reactions with propylene (CH2═C(H)CH3), maleic anhydride (ma, CH═CHCO(O)CO) and dimethyl maleate (dmm, CH3OCOCH═CHOCOCH3) led to the η2-alkene complexes [Ru(η5-C5H5)(η2-R1CH═CHR2)(PPh3)(L)]BPh4 (17-22). Treatment of the diazoalkane complexes 1 and 2 with acetylene CH≡CH under mild conditions (1 atm, room temperature) led to dipolar cycloaddition, affording the 3H-pyrazole complexes [Ru(η5-C5H5){η1-N═NC(Ar1Ar2)CH═CH}(PPh3){P(OMe)3}]BPh4 (24), whereas reactions with the terminal alkynes PhC≡CH and ButC≡CH gave the vinylidene derivatives [Ru(η5-C5H5){═C═C(H)R}(PPh3){P(OMe)3}]BPh4 (25, 26). The alkyl propiolates HC≡CCOOR1 (R1 = Me, Et) also reacted with complexes 2 to give the 3H-pyrazole complexes [Ru(η5-C5H5){η1-N═NC(Ar1Ar2)C(COOR1)═CH}(PPh3){P(OMe)3}]BPh4 (27, 28). The complexes were characterized by spectroscopy and by X-ray crystal structure determinations of [Ru(η5-C5H5){η1-N═C(CN)CH2C(Ph)(p-tolyl)NH}(PPh3){P(OMe)3}]BPh4 (19b), [Ru(η5-C5H5){η2-CH═CHCO(O)CO}(PPh3){P(OMe)3}]BPh4 (21), and [Ru(η5-C5H5){η1-N═NC(C12H8)CH═CH}(PPh3){P(OMe)3}]BPh4 (24c).
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Papers by Mattia Giacomello