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Synthesis of the Highly Reduced [Fe 6 C(CO) 15 ] 4– Carbonyl Carbide Cluster and Its Reactions with H + and [Au(PPh 3 )] +
Author(s) -
Bortoluzzi Marco,
Ciabatti Iacopo,
Cesari Cristiana,
Femoni Cristina,
Iapalucci Maria Carmela,
Zacchini Stefano
Publication year - 2017
Publication title -
european journal of inorganic chemistry
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 0.667
H-Index - 136
eISSN - 1099-0682
pISSN - 1434-1948
DOI - 10.1002/ejic.201700169
Subject(s) - chemistry , protonation , crystallography , octahedron , carbyne , nuclear magnetic resonance spectroscopy , cluster (spacecraft) , valence (chemistry) , x ray crystallography , rhenium , medicinal chemistry , stereochemistry , crystal structure , inorganic chemistry , catalysis , carbene , ion , organic chemistry , computer science , programming language , biochemistry , physics , optics , diffraction
The reduction of [Fe 6 C(CO) 16 ] 2– ( 1 ) with NaOH in DMSO or with Na/naphthalene in THF affords the highly reduced [Fe 6 C(CO) 15 ] 4– ( 2 ) monocarbide tetraanion. The molecular structure of 2 has been crystallographically determined as its [Et 4 N] 4 [Fe 6 C(CO) 15 ] · CH 3 CN salt, revealing an octahedral structure as expected for a hexanuclear cluster possessing 86 valence electrons. The stepwise protonation of 2 with strong acids such as HBF 4 · Et 2 O results first in the monohydride trianion [HFe 6 C(CO) 15 ] 3– ( 3 ) and then the purported dihydride dianion [H 2 Fe 6 C(CO) 15 ] 2– ( 4 ), as indicated by 1 H NMR spectroscopy. Both 3 and 4 are not stable enough to be isolated and rapidly decompose, yielding the parent dianion 1 . The reaction of 2 with a slight excess of Au(PPh 3 )Cl affords the aurated dianion [Fe 6 C(CO) 15 (AuPPh 3 ) 2 ] 2– ( 5 ), which has been isolated and structurally characterized as its [Et 4 N] 2 [Fe 6 C(CO) 15 (AuPPh 3 ) 2 ] · 2CH 3 CN salt. DFT calculations allowed us to study, from a computational point of view, the electronic features of the new compounds and possible reaction intermediates.