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MNE Nitrido Bridges with Transition Metal Nitrogen Multiple Bonds and E = Phosphorus, Sulfur, and Chlorine
Author(s) -
Dehnicke Kurt
Publication year - 2003
Publication title -
zeitschrift für anorganische und allgemeine chemie
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 0.354
H-Index - 66
eISSN - 1521-3749
pISSN - 0044-2313
DOI - 10.1002/zaac.200390136
Subject(s) - chemistry , homoleptic , rhenium , transition metal , ligand (biochemistry) , molybdenum , chlorine , sulfur , crystallography , tungsten , metal , medicinal chemistry , acetonitrile , redox , triple bond , monomer , nitrogen , inorganic chemistry , stereochemistry , polymer chemistry , double bond , organic chemistry , catalysis , biochemistry , receptor , polymer
A compilation is given on new syntheses, properties, and structures of complexes with M≡N—E ↔ M=N=E nitrido bridges with transition metal nitrogen multiple bonds and participation of the main group elements E of phosporus, sulfur, and chlorine. 1. MNP: This atomic sequence is realized in phosphoraneiminato complexes with transition metals in high oxidation states and termal bond of the (NPR 3 — ) ligand. A series of new complexes of this type is reported with M = zirconium, hafnium, molybdenum, tungsten, and rhenium, among these the homoleptic species [Hf(NPPh 3 ) 4 ] and [M(NPPh 3 ) 4 ] 2+ with M = Mo and W. Therefrom the isolobal complexes [:N≡Mo(NPPh 3 ) 3 ], [:O≡W(NPPh 3 ) 3 ] + , [(O) 2 Mo(NPPh 3 ) 2 ], and [(O) 3 Re(NPPh 3 )] are derived. 2. MNS: Adding to compounds with this atomic sequence, new complexes were developed on the basis of the functional ligand groups thionitrosyl ( a ), dinitridosulphate(II) ( b ), dinitridosulphate(IV) ( c ), and cyclothiazeno ( d ) ( cyclo ‐3, 5‐dithia‐2, 4, 6‐triazino):3. MNCl: Novel N‐chloroimido complexes of tungsten are described. [F 4 W≡N—Cl] 4 , which is tetrameric according to the IR spectrum, was obtained by direct fluorination from [Cl 4 W≡N—Cl] 2 or, surprisingly, from W(N)Cl 3 . With acetonitrile the monomeric molecular complex [CH 3 CN→WF 4 (≡N—Cl)] is formed. In an unexpected pathway K[F 5 W≡N—Cl] was obtained from a redox reaction of W(N)Cl 3 with trimethylstannyl fluoride in the presence of potassium fluoride. The ionic compound forms double layers with short Cl···F contacts.