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Transformation of organic molecules on the low‐valent {M(Ph 2 PCH 2 CH 2 PPh 2 ) 2 } moiety derived from trans ‐[M(N 2 ) 2 (Ph 2 PCH 2 CH 2 PPh 2 ) 2 ] or related complexes (M = MO, W)
Author(s) -
Seino Hidetake,
Mizobe Yasushi,
Hidai Masanobu
Publication year - 2001
Publication title -
the chemical record
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 1.61
H-Index - 78
eISSN - 1528-0691
pISSN - 1527-8999
DOI - 10.1002/tcr.1019
Subject(s) - moiety , chemistry , molecule , electrophile , stereochemistry , dissociation (chemistry) , metal , halogen , bond cleavage , group 2 organometallic chemistry , medicinal chemistry , cleavage (geology) , yield (engineering) , oxidative addition , crystallography , organic chemistry , alkyl , materials science , catalysis , composite material , fracture (geology) , metallurgy
A zero‐valent {M(Ph 2 PCH 2 CH 2 PPh 2 ) 2 } moiety (M = Mo, W) generated in situ by dissociation of the N 2 ligands in trans ‐[M(N 2 ) 2 (Ph 2 PCH 2 CH 2 PPh 2 ) 2 ] can activate π‐accepting organic molecules including isocyanides and nitriles, which undergo the electrophilic attack caused by a strong π‐donation from a zero‐valent metal center. Cleavage of a variety of C–X bonds (X = H, C, N, O, P, halogen) also occurs at their electron‐rich sites through oxidative addition to form reactive intermediates, which subsequently degradate to yield smaller molecules either bound to or dissociated from the metal center. The mechanism is substantiated unambiguously by isolation of numerous intermediate stages. © 2001 John Wiley & Sons, Inc. and The Japan Chemical Journal Forum Chem Rec 1:349–361, 2001