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Metal‐Template‐Directed Synthesis of Diphosphorus Compounds through Intramolecular Phosphinidene Additions
Author(s) -
Vlaar Mark J. M.,
van Assema Sander G. A.,
de Kanter Frans J. J.,
Schakel Marius,
Spek Anthony L.,
Lutz Martin,
Lammertsma Koop
Publication year - 2002
Publication title -
chemistry – a european journal
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 1.687
H-Index - 242
eISSN - 1521-3765
pISSN - 0947-6539
DOI - 10.1002/1521-3765(20020104)8:1<58::aid-chem58>3.0.co;2-5
Subject(s) - phosphinidene , intramolecular force , phosphole , chemistry , ligand (biochemistry) , bond cleavage , intermolecular force , thermal decomposition , trimer , stereochemistry , transition metal , crystallography , molecule , organic chemistry , dimer , catalysis , biochemistry , receptor
Heating the nonchelating cis ‐bis‐7‐phosphanorbornadiene‐[Mo(CO) 4 ] complex ( 13 ) results in the thermal decomposition of one of the 7‐phosphanorbornadiene groups. The phosphinidene thus generated adds intra molecularly to a C=C bond of the other ligand to give the novel diphosphorus complex 14 . This reaction constitutes a metal‐template‐directed synthesis. Likewise, the intramolecular phosphinidene addition to the C=C bond of a Mo‐phospholene ligand affords the diphos complex 18 . Its crystal structure exhibits an extremely small P‐Mo‐P bite‐angle for a five‐membered chelate ring. The similar intramolecular 1,2‐addition to a C=C bond of a phosphole ligand gives a highly strained, unstable intermediate product. Scission of its P−Mo bond generates a free coordination site, which is then occupied by either CO or a phosphole to yield complexes 22 and 23 , respectively. The analogous inter molecular addition of [PhPW(CO) 5 ] to a [phosphole‐W(CO) 5 ] complex gives the di‐[W(CO) 5 ] complexed adduct 28 . The directing effect of the metal on the intra ‐ and inter molecular additions is discussed.