Multiple Bonds between Main-Group Elements and Transition Metals. 67. Synthesis of Novel Half-Sandwich Rhenium(V) Complexes of Mono- and Bidentate Sulfur-Containing Ligands: X-ray Crystal Structure of the Xanthate-S,S Complex (ή5-C5Me5)ReCl3(S2CO-c-C6H11)

Janos Takacs, Paul Kiprof, Georg Weichselbaumer, Wolfgang A. Herrmann

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Abstract

The d2 rhenium(V) complex (ή6-C6Meg)Re(0)Cl2 (1) reacts with thiolates under ambient conditions to yield the disubstituted complexes 2 of composition (ή-C5Me5)Re(0)(SR1)2 [R1= ethyl (2a), phenyl (2c), 2-pyridyl (2d)]. Bulkier ligands such as 2-methylpropane-2-thiolate give rise to formation of monosubstituted complexes, e.g., (ή5-C5Me5)Re(0)(Cl)(S-t-C4H9) (3) at room temperature, while disubstitution occurs in refluxing toluene with formation of compound 2b (R1= τ-C4H9). The reactions of (ή6-C5Meg)ReCl4(4) with sodium cyclohexylxanthate or with lithium Nβ-diethyldithiocarbamate yield monosubstituted derivatives of formula (ή-C5Me5ReCl3CR2) (5a,b). A single-crystal X-ray diffraction study of the xanthate complex (Å5-C5Me5)ReCl3(S2CO-c-C6H11) (5a, R2= 0-c-C6Hn) shows an octahedral coordination sphere around the rhenium, with the sulfur atoms of the bidentate ligand being bonded to the metal atom in an equatorial and in an axial position.

Original languageEnglish (US)
Pages (from-to)2394-2398
Number of pages5
JournalOrganometallics
Volume8
Issue number10
DOIs
StatePublished - Oct 1 1989

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