Premium
Triferriothioxophosphoranes: First Structural Characterization of a μ 3 ‐P=S Complex
Author(s) -
Lorenz IngoPeter,
Pohl Wolfgang,
Polborn Kurt
Publication year - 1996
Publication title -
chemische berichte
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 0.667
H-Index - 136
eISSN - 1099-0682
pISSN - 0009-2940
DOI - 10.1002/cber.19961290104
Subject(s) - chemistry , photodissociation , deprotonation , sulfur , transition metal , ligand (biochemistry) , mass spectrometry , medicinal chemistry , stereochemistry , crystallography , metal , decomposition , photochemistry , organic chemistry , catalysis , ion , biochemistry , receptor , chromatography
Abstract The P‐H‐functional triferriophosphonium salts [{CpFe‐(CO) 2 } 3 PH] 2 FeCl 4 ( 1 ) and [{μ‐CO(CpFeCO) 2 }{CpFe‐(CO) 2 }PH] 2 FeCl 4 ( 4 ) are easily deprotonated by DBU to the corresponding unstable triferriophosphanes 2, 5 , which subsequently are oxidized by sulfur to the triferriophosphane sulfides {CpFe(CO) 2 } 3 P=S ( 3 ) and {μ‐CO(CpFeCO) 2 }{CpFe‐(CO) 2 }P=S ( 6 ), respectively. The photolysis of 3 results only in its decomposition by elimination of [CpFe(CO) 2 ] 2 , whereas the photolysis of 6 cleaves off one CO ligand to give the new spiro compound (CpFeCO)(μ‐η 2 ‐PS){μ‐CO(CpFeCO) 2 } ( 7 ), where the P=S unit is η 2 ‐bonded to the 15‐electron CpFeCO fragment, and the phosphorus atom bridges two 17‐electron fragments. Compound 7 shows a new coordination mode of the PS unit where sulfur is also bound to one of the metal atoms. Compounds 6 and 7 can be regarded as first examples of a new class of PS complexes of transition metals. All compounds were characterized by IR, 31 P{ 1 H}‐ and 13 C{ 1 H}‐NMR spectroscopy as well as mass spectrometry; for 6 the X‐ray analytical data are given.