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Ionic‐Liquid‐Based Synthesis of the Germanium‐Iron Carbonyls FeI 4 {GeI 3 Fe(CO) 3 } 2 and (GeI 3 ) 2 Fe(CO) 4
Author(s) -
Wolf Silke,
Feldmann Claus
Publication year - 2017
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.201600380
Subject(s) - octahedron , crystallography , ionic liquid , infrared spectroscopy , thermogravimetry , chemistry , ionic bonding , germanium , oxygen , crystal structure , intermolecular force , analytical chemistry (journal) , molecule , inorganic chemistry , ion , organic chemistry , catalysis , silicon
Dark red and brick red transparent crystals of FeI 4 {GeI 3 Fe(CO) 3 } 2 ( 1 ) and (GeI 3 ) 2 Fe(CO) 4 ( 2 ) were obtained by reacting GeI 4 and Fe 2 (CO) 9 or Fe 3 (CO) 12 in a mixture of [BMIM]Cl and AlCl 3 as ionic liquid (BMIm = 1‐butyl‐3‐methylimidazolium). According to X‐ray structure analysis based on single crystals, the title compounds exhibit cluster units with Fe–Ge bonds. FeI 4 {GeI 3 Fe(CO) 3 } 2 consists of two GeI 2 I 1/2 ‐Fe(CO) 3 I 2/2 units that are interlinked by a distorted octahedral FeI 6/2 group. (GeI 3 ) 2 Fe(CO) 4 consists of two GeI 3 units that are connected by a square planar Fe(CO) 4 group with a linear Ge–Fe–Ge unit. Depending on the synthesis conditions, interestingly, (GeI 3 ) 2 Fe(CO) 4 crystallizes either in P 2 1 / n ( 2a ) or in P 1 ( 2b ). 2a exhibits a more dense packing, whereas 2b exhibits shorter intermolecular I–I distances. Both title compounds are temperature labile and highly sensitive to oxygen, moisture and illumination, including X‐ray irradiation. They decompose with release of CO in absence of certain CO atmosphere. In addition to crystal structure analysis the compounds were characterized by energy dispersive X‐ray (EDX) analysis, thermogravimetry (TG) and infrared spectroscopy (FT‐IR).