Übergangsmetall‐Thioketen‐Komplexe, III. Synthese und Struktur von Thioketen‐Komplexen von Hexacarbonylchrom, Hexacarbonylwolfram und Tricarbonyl(cyclopentadienyl)mangan

Abstract

Stabile Dialkylthioketene (la,b) reagieren photochemisch mit Cr(C0)6, W(CO), und (C,H,)Mn(CO), zu den Komplexen 2 und 3, in denen der Ligand iiber das Schwefelatom koordiniert ist. Die Struktur des Mangankomplexes 2c wurde rontgenographisch bestimmt. Transition Metal Thioketene Complexes, 111 I ) Synthesis and Structure of Thioketene Complexes from Hexacarbonylchromium, Hexacarbonyltungsten, and Tricarbonyl(cyclopentadieny1)manganeseStable dialkylthioketenes react photochemically with Cr(C0)6, W(CO),, and (C,H,)Mn(CO), to give the complexes 2 and 3 with the ligand coordinated via the sulfur atom. The structure of the manganese complex 2c has been determined by X-ray diffraction.Bisher sind nur wenige Thioketen-Metallkomplexe beschrieben worden l -z ) , da die meisten Thioketene (1) thermolabil sind und schnell dimerisieren3).Eine Stabilisierung des Heterokumulensystems lafit sich jedoch durch Einfuhrung sterisch anspruchsvoller Reste R erreichen. Nach diesem Prinzip wurde eine Reihe von Dialkylthioketenen zuganglich 4), die eine eingehendere Untersuchung dieser Substanzklasse ermoglichen.

Molybdenum and Tungsten η2-Alkyne-1-thio Complexes Acting as Sulfur Donors in Homoleptic Werner Type Complexes with Nickel(II) and Palladium(II)

“…However, according to resonance structure A , the thioketenyl character is evident by the distinctly shorter Mo−C2 bond (2.020 Å) compared with that of Mo−C1 (2.143 Å). Interestingly, stable thioketenes form either η 1 - S or η 2 - SC complexes. , …”

“…Interestingly, stable thioketenes form either η 1 -S or η 2 -SC complexes. 28,29 With regard to the rotation of the η 2 -C,C-bound ligand at the metal center, 3a/3b behave in solution like typical alkyne complexes. 30 In the 1 H NMR spectrum of 3a at -60 °C, two CH 2 resonances at 5.20 and 3.26 ppm exhibit comparable intensity.…”

Spontaneous Formation of an η2‐C, S‐Thioketene Complex in Pursuit of Tungsten(IV)‐Sulfanylalkyne Complexes

“…The alternative η 2 ‐C, C′ mode ( C ) is regularly observed in well‐understood intermediate products on the path to acdt 2– complexes,6 while first examples were originally described by Hill 7. The third type, an end‐on η 1 ‐S motif ( D ) was reported by Behrens , whose studies involve the coordination behavior of certain stable and therefore sterically encumbered thioketenes 8…”