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Isoelectronic Relationships in Cluster Chemistry: Nucleophilic Addition to a Vinylidene Ligand
Author(s) -
Albiez Thomas,
Vahrenkamp Heinrich
Publication year - 1987
Publication title -
angewandte chemie international edition in english
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 5.831
H-Index - 550
eISSN - 1521-3773
pISSN - 0570-0833
DOI - 10.1002/anie.198705721
Subject(s) - electrophile , nucleophile , chemistry , cluster (spacecraft) , reactivity (psychology) , ligand (biochemistry) , atom (system on chip) , polarity (international relations) , stereochemistry , medicinal chemistry , metal , ion , center (category theory) , computational chemistry , crystallography , organic chemistry , catalysis , medicine , biochemistry , alternative medicine , receptor , pathology , computer science , embedded system , cell , programming language
The polarity of vinylidene ligands is reversed in going from mononuclear to polynuclear vinylidene complexes. The electrophilic center is shifted from the metal‐bound α‐C atom to the terminal β‐C atom. An example is provided by the complex 1 , which reacts with PMe 3 to give 2 . The pattern of reactivity can be understood in terms of isoelectronic considerations, for 1 corresponds to the cluster‐stabilized carbenium ion [Co 3 (CO) 9 (μ 3 ‐CCH 2 )] ⊕ , whereas 2 is an analogue of the very stable cluster [Co 3 (CO) 9 (μ 3 ‐CR)].