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Insight into the Reaction of a Dinuclear Phosphinidene Complex with Nitriles
Author(s) -
Seidl Michael,
Weinzierl Rudolf,
Timoshkin Alexey Y.,
Scheer Manfred
Publication year - 2016
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/chem.201504954
Subject(s) - phosphinidene , benzonitrile , chemistry , aniline , reactivity (psychology) , medicinal chemistry , nitrosobenzene , derivative (finance) , stereochemistry , nuclear magnetic resonance spectroscopy , organic chemistry , medicine , alternative medicine , pathology , financial economics , economics , catalysis
The phosphinidene complex [Cp*P{W(CO) 5 } 2 ] ( 1 ; Cp*=C 5 Me 5 ) reacted with malononitrile to give the 1,2‐dihydro‐1,3,2‐diazaphosphinine derivative 2 . The reaction of 1 with 1,4‐benzodinitrile gave [1,4‐{{W(CO) 5 } 2 P‐N=C(Cp*)} 2 (C 6 H 4 )] ( 3 ), the first example of a cumulene‐like aminophosphinidene complex. The reaction of 1 with aniline gave the aminophosphinidene complex [(Ph)N(H)P{W(CO) 5 } 2 ] ( 4 ). To compare the reactivity of benzonitrile and aniline with 1 , the phosphinidene complex 1 was reacted with three different isomers of aminobenzonitrile (2‐, 3‐, and 4‐aminobenzonitrile). These reactions gave an insight into the reaction pathway of 1 with benzonitrile derivatives. Compounds 5 , 6 a , 6 b , and 7 , which are derivatives of 1,2‐dihydro‐1,3,2‐diazaphosphinine or benzo‐2 H ‐1,2‐azaphospholes, were, as well as all other products, characterized by mass spectrometry, NMR and IR spectroscopy, and X‐ray structure analysis.