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Title: Reactions of aminophosphines and aminobis(phosphines) with aldehydes and ketones: coordination complexes of the resultant aminobis(alkylphosphineoxides) with cobalt, uranium, thorium and gadolinium salts: crystal and molecular structures of Ph2P(O)CH(C6H4OH-o)N(H)Ph, Ph2P(O)CH(OH)C6H4OH-o and Ph2P(O)N(H)Ph
Keywords: Bonds
Coordination Complexes
Crystal Structure
Issue Date: 2005
Publisher: Elsevier
Citation: Polyhedron 24(13), 1641-1650
Abstract: The reaction of aminophosphines and aminobis(phosphines) with aldehydes leads to either insertion of carbon fragments into the P(III)–N bonds or formation of α-hydroxyphosphine oxides through P(III)–N bond cleavage. Reaction of 1,2-C6H4{N(H)PPh2}2 with paraformaldehyde gives the P(III)–N bond inserted product 1,2-C6H4{N(H)CH2P(O)Ph2}2, whereas 1,3-C6H4{N(H)PPh2}2 forms an analogous product but with an additional methylene group inserted between the two nitrogen centers through nucleophilic addition to form a bicyclic derivative, 1,3-C6H4{Ph2P(O)CH2N(μ-CH2)NCH2P(O)Ph2}. Reactions of Ph2PN(H)Ph with aromatic aldehydes, RCHO (R = C6H4OH-o, 5-BrC6H3OH-o, (η5-C5H5)Fe(η5-C5H4–)) lead to the insertion of ‘RCH’ into the P(III)–N bond to give Ph2P(O)CH(R)N(H)Ph. The reactions of aminobis(phosphine), Ph2PN(nBu)PPh2 with both aromatic and aliphatic aldehydes lead to the formation of α-hydroxy phosphine oxide derivatives of the type Ph2P(O)CH(R)OH, through P(III)–N bond cleavage. The N-bridged bis(phosphine oxide) nPrN(CH2P(O)Ph2)2 readily forms chelate complexes with U(VI), Th(IV) and Gd(III) derivatives.
ISSN: 0277-5387
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