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Please use this identifier to cite or link to this item: http://dspace.library.iitb.ac.in/jspui/handle/10054/3908

Title: Insertion of carbon fragments into P(III)-N bonds in aminophosphines and aminobis(phosophines): Synthesis, reactivity and coordination chemistry of resulting phosphine oxide derivatives. Crystal and molecular structures of (Ph2P(O)CH2)(2)NR (R = Me, Pr-n, Bu-n), Ph2P(O)CH(OH)Pr-n, and cis-[MoO2Cl2{(Ph2P(O)CH2)(2)NEt-kappa O,kappa O}]
Authors: PRIYA, S
BALAKRISHNA, MS
MAGUE, JT
MOBIN, SM
Keywords: transition-metal chemistry
phosphorus based ligands
polyfunctional molecules
organometallic derivatives
complexes
bis(diphenylphosphanyl)amine
bis(phosphino)amines
diphosphazanes
ruthenium(ii)
palladium(ii)
Issue Date: 2003
Publisher: AMER CHEMICAL SOC
Citation: INORGANIC CHEMISTRY, 42(4), 1272-1281
Abstract: Reactions of N-aryl and N-alicyclic derivatives of aminophosphines with paraformaldehyde lead to methylene insertion into P-N bond followed by oxidation of phosphorus from the P(III) to P(V) state. When N-alkyl derivatives are reacted with paraformaldehyde, dimerization takes place to afford bis(phosphine oxide)s of the type Ph2P(O)CH2N(R)CH2P(O)Ph-2 (R = Me, Pr-n, Bu-n). Aminobis(phosphines) also undergo methylene insertion when treated with paraformaldehyde to give bis(phosphine oxides) Ph2P(O)CH2N(R)CH2P(O)Ph-2 (R = Me, Et, Pr-n, Pr-i, Bu-n) in good yield. The reaction of aminophosphines with aromatic aldehydes ArCHO leads to insertion of "ArCH" into the P-N bond to give Ph2P(O)CH(R)N(H)Ph (R = C6H5, furfuryl, o-C6H4OH), but with aliphatic aldehydes such as butanal, P-N bond cleavage takes place to afford alpha-hydroxy phosphine oxide. The reaction of aminobis(phosphines) with both aromatic and aliphatic aldehydes leads to the formation of alpha-hydroxy phosphine oxides through P-N bond cleavage whereas the reaction with furfural leads to the P-N bond insertion. The structure of the alpha-hydroxy derivative Ph2P(O)CR(H)(OH)Pr-n shows intermolecular hydrogen bonding between OH and P=O oxygen. The phosphine oxide derivatives act as bidentate ligands and form chelate complexes with Co(II), Mo(VI), Th(IV), and U(VI) derivatives. The crystal structure of the molybdenum complex, cis-[MoO2Cl2{(OPPh2CH2)(2)NEt-kappaO,kappaO}], shows the distorted octahedral geometry around Mo with two oxo groups cis to each other.
URI: http://dx.doi.org/10.1021/ic026118t
http://dspace.library.iitb.ac.in/xmlui/handle/10054/3908
http://hdl.handle.net/10054/3908
ISSN: 0020-1669
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