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Reactivity of Cyanide and Thiocyanate Towards the Nitrosyl Carbonyl [Co(CO) 3 (NO)]
Author(s) -
Böttcher HansChristian,
Graf Marion,
Mayer Peter
Publication year - 2020
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.202000182
Subject(s) - chemistry , reactivity (psychology) , ligand (biochemistry) , thiocyanate , salt (chemistry) , yield (engineering) , cyanide , medicinal chemistry , crystal structure , metal carbonyl , crystallography , metal , stereochemistry , inorganic chemistry , organic chemistry , medicine , biochemistry , materials science , receptor , alternative medicine , pathology , metallurgy
The reaction of equimolar amounts of [Co(CO) 3 (NO)] and [PPN]CN, PPN + = (PPh 3 ) 2 N + , in THF at room temperature resulted in ligand substitution of a carbonyl towards the cyanido ligand presumably affording the complex salt PPN[Co(CO) 2 (NO)(CN)] as a reactive intermediate species which could not be isolated. Applying the synthetic protocol using the nitrosyl carbonyl in excess, the title reaction afforded unexpectedly the novel complex salt PPN[Co 2 (μ‐CN)(CO) 4 (NO) 2 ] ( 1 ) in high yield. Because of many disorder phenomena in crystals of 1 the corresponding NBu 4 + salt of 1 has been prepared and the molecular structure of the dinuclear metal core in N n Bu 4 [Co 2 (μ‐CN)(CO) 4 (NO) 2 ] ( 2 ) was determined by X‐ray crystal diffraction in a more satisfactory manner. In contrast to the former result, the reaction of [PPN]SCN with [Co(CO) 3 (NO)] yielded the mononuclear complex salt PPN[Co(CO) 2 (NO)(SCN‐κ N )] ( 3 ) in good yield whose molecular structure in the solid was even determined and its composition additionally confirmed by spectroscopic means.