Detlev Wormsbächer

Übergangsmetall-thioketen-komplexe: V. Darstellung, struktur und eigenschaften von thioketen-cobalt-komplexen

The stable thioketenes I react with Co2(CO)8 to form the dinuclear complexes (thioketene)2Co2(CO)4 (II). The structure of such a complex (IIa) has been determined by X-ray diffraction. The reaction of thioketenes I with (C5H5)Co(CO)2 gives a mixture of (thioketene)(C5H5)Co(CO) (V) and (thioketene)2(C5H5)2Co2 (VI) complexes. Complexes VI are also formed by the reaction of (C5H5)Co(C2H4)2 with thioketenes I. The displacement of CO from V by phosphanes yields (thioketene)(C5H5)Co(PR3) (VII) complexes which can be methylated with CH3I to give (thioketene-SCH3)(C5H5)Co(PR3)+I− (VIII) salts. The structures of all the types of complexes VI and VIII have been determined by an X-ray diffraction study. Die stabilen Thioketene I reagieren mit Co2(CO)8 unter Bildung der zweikernigen Komplexe (Thicketen)2Co2(CO)4 (II). Die Struktur eines solchen Komplexes (IIa) wurde rontgenographisch bestimmt. Die Reaktion der Thioketene I mit (C5H5)Co(CO)2 fuhrt zu einer Mischung der Komplexe (Thioketen)(C5H5)Co(CO) (V) und (Thioketen)2(C5H5)2Co2 (VI). Die Komplexe VI bilden sich auch bei der Reaktion von (C5H5)Co(C2H4)2 mit den Thioketenen I. Ersatz des COs in V durch Phosphane fuhrt zu den Komplexen (Thioketen)(C5H5)Co(PR3) (VII), die mit CH3I methyliert werden konnen, wobei sich die Salze (Thioketen-SCH3)(C5H5)Co(PR3)+I− (VIII) bilden. Die Struktur je eines Komplexes vom Typ VI und VIII wurde rontgenographisch bestimmt.

Ubergangsmetall-thioketen-komplexe: VIII. Reaktionen der cluster-komplexe (thioketen)Fe2(CO)6, mit phosphanen: Struktur und eigenschaften von thioketen-eisen-komplexen

Abstract The cluster complex (thioketene)Fe 2 CO) 6 ,; (IIa) reacts with CO to give (thioketene)Fe 2 (CO) 7 (IIIa). Equally phosphanes (PR 3 ) an cleave the cluster II to form complexes of the type (thioketene)Fe 2 (CO) 6 PR 3 (IV) and (thioketene)Fe 2 (CO) 6 ,(CH 2 PPh 3 ) (VIII). The chelate phosphanes dppm and dppe react with II to give the opened and closed clusters (thioketene)Fe 2 CO 5 (DPPE) (μ-dppm) (X), (thioketene)Fe 2 (CO) 4 (μ-dppe) (XI), (thioketene)Fe 2 (CO) 5 (dppe) (XIII), (thioketene)Fe 2 (CO) 4 (μ-dppe) (XV) and thioketene)Fe 2 (CO) ( μ-dppe) (XVI), according to the reaction conditions. The structures of four of the complexes (IVa, Villa, X, and XIIIb) have been determined by X-ray diffraction.

Übergangsmetall-thioketen-Komplexe. VI: Synthese und Struktur von Bis(cyclopentadienyl)(thioketen)vanadium-Komplexen

Abstract Addition of the “carbenoid” [(C 5 H 5 ) 2 V] to thioketenes [R 2 CCS] leads to [(C 5 H 5 ) 2 V(R 2 CCS)] complexes containing an η 2 -(CS) bonded thioketene ligand, as confirmed by X-ray analysis.

Übergangsmetall-heteroallen-komplexe: XXVI. Synthese und Struktur von zweikernigen molybdän-thioketen-komplexen

The thioketene C11H18S (3) reacts with [Mo2(CO)4(C5H5)2] to give the complex [Mo2(CO)4(C5H5)2(C11H18S)] (1b). A mixed thioketene-ketenimine-Mo-complex (2c) was synthesized by reaction of the ketenimine complex 1a with the thioketene C11H18S (3). The structures of 1b and 2c were determined by X-ray diffraction studies.

Übergangsmetall-Heteroallen-Komplexe. XIV: Synthese und Struktur von μ-DI-t-butylthioketen-bis(dicarbonylcyclopentadienyl-mangan)

Zusammenfassung The reaction of di-t-butylthioketene [R 2 CCS] with [Mn(CO) 2 (THF)(C 5 H 5 )] leads to the dinuclear complex {μ(R 2 CCS)[Mn(CO) 2 (C 5 H 5 )] 2 } in low yield, which was structurally characterized by an X-ray analysis.