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Hydride Migration from a Triangular Face to a Tetrahedral Cavity in Tetranuclear Iron Carbonyl Clusters upon Coordination of [AuPPh 3 ] + Fragments
Author(s) -
Bortoluzzi Marco,
Ciabatti Iacopo,
Femoni Cristina,
Hayatifar Mohammad,
Iapalucci Maria Carmela,
Longoni Giuliano,
Zacchini Stefano
Publication year - 2014
Publication title -
angewandte chemie international edition
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 5.831
H-Index - 550
eISSN - 1521-3773
pISSN - 1433-7851
DOI - 10.1002/anie.201403538
Subject(s) - hydride , chemistry , crystallography , cluster (spacecraft) , tetrahedron , metal , tetrahedral molecular geometry , crystal structure , stereochemistry , organic chemistry , computer science , programming language
Metal hydrides are of fundamental importance in chemistry, both as solid‐state materials and molecular compounds. The first low‐valent molecular metal cluster containing an interstitial four‐coordinate hydride in a tetrahedral site is decribed, which undergoes hydride migration from the surface to the tetrahedral cavity of the cluster upon coordination of a [AuPPh 3 ] + fragment. The [HFe 4 (CO) 12 (AuPPh 3 ) 2 ] − mono‐anion, which contains a surface μ 3 ‐H, was obtained from the reaction of [HFe 4 (CO) 12 ] 3− with two equivalents of [Au(PPh 3 )Cl]. This is, in turn, transformed into the neutral [HFe 4 (CO) 12 (AuPPh 3 ) 3 ] upon addition of a third [AuPPh 3 ] + fragment, with concomitant migration of the unique hydride from the surface of the cluster to its tetrahedral cavity. All of these species have been fully characterized in solution by means of IR and multinuclear NMR spectroscopy, and in the solid state by single‐crystal X‐ray diffractometry.