Premium
Binuclear CpV, Cp*V, and Cp*Ta Complexes containing Organochalcogenolato Bridges, μ‐ER (E = Sulfur, Selenium, Tellurium; R = Methyl, Phenyl, and Ferrocenyl)
Author(s) -
Herberhold Max,
Peukert Jürgen,
Krüger Michaela,
Daschner Daniela,
Milius Wolfgang
Publication year - 2000
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/(sici)1521-3749(200006)626:6<1289::aid-zaac1289>3.0.co;2-o
Subject(s) - chemistry , stereochemistry , crystallography , cyclopentadienyl complex , bathochromic shift , molecule , triclinic crystal system , medicinal chemistry , crystal structure , catalysis , fluorescence , biochemistry , physics , organic chemistry , quantum mechanics
Photolysis of the halfsandwich tetracarbonylmetal complexes CpV(CO) 4 , Cp*V(CO) 4 and Cp*Ta(CO) 4 in solution in the presence of di(organyl)dichalcogenides E 2 R 2 (E = S, Se, Te; R = Me, Ph, Fc) leads to diamagnetic doubly organochalcogenolato‐bridged compounds, [Cp () M(CO) 2 (μ‐ER)] 2 . According to the X‐ray structure determinations carried out for [CpV(CO) 2 (μ‐TeMe)] 2 , [Cp*V(CO) 2 (μ‐TePh)] 2 and [Cp*Ta(CO) 2 (μ‐SPh)] 2 , the molecular framework consists of a folded M 2 (μ‐ER) 2 ring with the cyclopentadienyl ligands in cis ‐configuration and the organyl substituents R in a syn ‐equatorial arrangement, thus forming a bowl‐shaped molecule with the four terminal CO ligands protruding into the inner sphere. The M…M distances (in the range between 305 and 330 pm) are not considered to indicate direct bonding interactions. The vanadium complexes [Cp () V(CO) 2 (μ‐ER)] 2 are completely decarbonylated in the presence of an excess of E 2 R 2 in boiling toluene, and in many cases the paramagnetic quadruply‐bridged products, [CpV(μ‐ER) 2 ] 2 , can be isolated.