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Selective P 4 Activation by a Highly Reduced Cobaltate: Synthesis of Dicobalt Tetraphosphido Complexes
Author(s) -
Pelties Stefan,
Maier Thomas,
Herrmann Dirk,
de Bruin Bas,
Rebreyend Christophe,
Gärtner Stefanie,
Shenderovich Ilya G.,
Wolf Robert
Publication year - 2017
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.201603296
Subject(s) - chemistry , acenaphthene , acetonitrile , oxidizing agent , diethyl ether , yield (engineering) , medicinal chemistry , electron paramagnetic resonance , ligand (biochemistry) , cyclooctadiene , organic chemistry , catalysis , biochemistry , materials science , physics , receptor , nuclear magnetic resonance , pyrene , metallurgy
Although the chemistry of transition metal polyphosphide anions has attracted significant attention, there are few reports of studies in which such species have been synthesized directly from white phosphorus. [K(OEt 2 ) 2 {Co(BIAN)(cod)}] ( 1 , BIAN=1,2‐bis(2,6‐diisopropylphenylimino)acenaphthene, cod=1,5‐cyclooctadiene), which is readily prepared by ligand exchange from [K(thf) x {Co(cod) 2 }], reacts with P 4 to afford [{K(thf)} 2 {(BIAN)Co} 2 (μ‐η 4 :η 4 ‐P 4 )] ( 2 a ) in 61 % yield (isolated product). [{K(OEt 2 )} 2 {(BIAN)Co} 2 (μ‐η 4 :η 4 ‐P 4 )] ( 2 b ) and [K([18]crown‐6)(MeCN)] 2 [{(BIAN)Co} 2 (μ‐η 4 :η 4 ‐P 4 )] ( 2 c ) were obtained by recrystallizing 2 a from diethyl ether and acetonitrile (and using [18]crown‐6 in case of 2 c ). Oxidation of 2 a with [Cp 2 Fe]BAr F 4 (one equivalent) and subsequent recrystallization of the product from different solvents gave [K(OEt 2 ){(BIAN)Co} 2 (μ‐η 4 :η 4 ‐P 4 )] ( 3 a ) and [K(dme) 4 ][{(BIAN)Co} 2 (μ‐η 4 :η 4 ‐P 4 )] ( 3 b ; dme=1,2‐dimethoxyethane). Neutral [{(BIAN)Co} 2 (μ‐η 4 :η 4 ‐P 4 )] ( 4 ) was obtained in moderate yield by oxidizing 2 a with two equivalents of [Cp 2 Fe]BAr F 4 . The new complexes were characterized by NMR, EPR (in the case of 3 a ), and UV/Vis spectroscopy, and elemental analysis. The molecular structures revealed by X‐ray crystallography display planar cyclic or open‐chain P 4 4− units sandwiched between {(BIAN)Co} fragments.