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Please use this identifier to cite or link to this item: http://dspace.library.iitb.ac.in/jspui/handle/10054/1043

Title: Half-sandwich ruthenium(II) complexes of aminophosphines: synthesis, structures and catalytic applications in C–C coupling reactions between styrenes and diphenyldiazomethane
Authors: SRINIVASAN, PRIYA
BALAKRISHNA, MS
SHAIKH, MOBIN M
MCDONALD, ROBERT
Keywords: derivatives
x-ray diffraction
crystal structure
Issue Date: 2003
Publisher: Elsevier
Citation: Journal of Organometallic Chemistry 688(1-2), 227-235
Abstract: The half-sandwich Ru(II) complexes of the type [CpRu(PPh2N(H)R)(PPh3)Cl], [CpRu(PPh2N(H)R)2Cl] (R=Ph, C6H11) and [CpRu(PPh2N(R′)PPh2-κP,κP)(PPh3)]Cl (R′=Et, nPr, iPr, nBu), were synthesized and the structures of complexes [CpRu(PPh2N(H)Ph)(PPh3)Cl] and [CpRu(PPh2N(H)Ph)2Cl] were confirmed by single crystal X-ray diffraction studies. All ruthenium complexes were employed in the cyclopropanation reaction of styrene derivatives in the presence of diphenyldiazomethane. All complexes afford 1,1,3,3-tetraphenyl cyclobutane along with cyclopropane derivatives; complex, [CpRu(PPh2N(nBu)PPh2-κP,κP)(PPh3)]Cl shows better selectivity in the formation of 1,1,2-triphenylcyclopropane. In all reactions appreciable amounts of cyclopropanation products and metathesis products, 1,2-diphenylcyclopropane and 1,1-diphenylethene were obtained along with 1,1,3-triphenylpropene derivatives. The variable temperature NMR studies have suggested that the cyclopropanation reactions in the presence of ionic complex, [CpRu(PPh2N(R′)PPh2-κP,κP)(PPh3)]Cl proceeds via carbene intermediate, [CpRu(=CPh2)(PPh2N(R′)PPh2-κP)(PPh3)]Cl.
URI: http://dx.doi.org/10.1016/j.jorganchem.2003.09.020
http://hdl.handle.net/10054/1043
http://dspace.library.iitb.ac.in/xmlui/handle/10054/1043
ISSN: 0022-328X
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