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Spontaneous Formation of an η 2 ‐C, S‐Thioketene Complex in Pursuit of Tungsten(IV)‐Sulfanylalkyne Complexes
Author(s) -
Helmdach Kai,
Villinger Alexander,
Seidel Wolfram W.
Publication year - 2015
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/zaac.201500576
Subject(s) - dichloromethane , alkyne , moiety , tungsten , chemistry , boron , crystallography , carbyne , stereochemistry , solvent , medicinal chemistry , x ray crystallography , diffraction , carbene , organic chemistry , physics , catalysis , optics
The oxo tungsten(IV) alkyne complexes [Tp′W(O)(I)(η 2 ‐C 2 Ph 2 )] ( 1 ), [Tp′W(O)(I){η 2 ‐C 2 (SC 2 H 4 SiMe 3 ) 2 }] ( 2 ), and [Tp′W(O)(I){η 2 ‐C 2 (SBn) 2 }] ( 3 ) [Tp′ = hydridotris(3, 5‐dimethylpyrazolyl)borate, Bn = benzyl] were synthesized from [Tp′W(O)(CO)(I)]. All three compounds were fully characterized including structure determination by X‐ray diffraction analysis. Further elucidation of these reactions led to the isolation of several by‐products including an unexpected tungsten(IV) thioketene complex [Tp′W(O)(I){η 2 ‐S = C=C(H)(SBn)}] ( 4 ), which is formed by removal of one Bn group from the alkyne, and dinuclear [Tp′W(O)(I)] 2 (μ‐O) ( 6 ). Both complexes were also fully characterized. X‐ray diffraction analysis reveals an η 2 ‐S, C side‐on binding mode for 4 and a planar O–W–O–W–O moiety for 6 . In addition, by changing the solvent from THF to dichloromethane formation of the chiral dihalogen complex [Tp′W(O)(Cl)(I)] ( 5 ) was proven.