Synthesis and reactions of some new thiocarboxamido complexes of manganese and molybdenum carbonyls

Metallathiirenes. 4.1 Thioaroyl Complexes of Molybdenum(II) and Tungsten(II)

“…The salts [Mo(η 2 -MeSCR)(CO) 2 {HB(pz) 3 }]BF 4 (R = R 2 , R 3 ) were also obtained from the reactions of the carbyne complexes [Mo(⋮CR)(CO) 2 {HB(pz) 3 }] with [MeSSMe 2 ]BF 4 . Notably, although the thiocarbamoyl complex [Mo(η 2 -SCNMe 2 )(CO) 2 (η-C 5 H 5 )] may be alkylated on sulfur with [Me 3 O]BF 4 to provide [Mo(η 2 -MeSCNMe 2 )(CO) 2 (η-C 5 H 5 )]BF 4 , the corresponding reaction of [Mo(η 2 -SCNMe 2 )(CO) 2 {HB(pz) 3 } with [Et 3 O]BF 4 fails 9 Reactions of Thioaroyl Complexes with Electrophiles a a R = C 6 H 4 Me-4, C 6 H 4 OMe-4 (not all combinations). …”

Synthesis and Crystal Structures of the Molybdenum(II) Complexes with the N,N‐dimethylthiocarbamoyl Containing Ligand: Crystal Structures of [Mo(CO)2(η2‐S2COEt)(η2‐SCNMe2)(PPh3)] and [Mo(CO)2(η2‐S2CNC4H8)(η2‐SCNMe2)(PPh3)]

“…Elemental analyses and X-ray diffraction studies were carried out at the Regional Center of Analytical Instrument located at the National Taiwan University. Mo(CO) 6 …”

“…5 These complexes have been prepared from the reaction of metal carbonylates with N,N-dimethylthiocarbamoyl chloride, Me 2 NC(=S)Cl, via nucleophilic displacement of chloride, 6 nucleophilic attack by an amine on the electrophilic thiocarbonyl complex, 7 electrophilic attack at a coordinated isothiocyanate, 8 reaction of hydrosulfide with haloaminocarbene 9 or isonitrile 10 ligands, cleavage of the dithiocarbamate ligand, 11 or C-H activation of thioformamides. 12 Oxidative addition 13 of both chloride and N,Ndimethylthiocarbamoyl ligands to the metal complex are most generally used and relevant to the work described herein.…”

Synthesis of carbene complexes by reaction of platinum thiocarbamoyl and thio ester complexes with electrophiles

“…Reaction of 1 with benzyl bromide or allyl bromide occurs slowly over a period of about 1 hr at 25". Treatment of the reaction solution with AgBF4 causes precipitation of AgBr allowing the carbene cations to be isolated as the (BF4)-salts From the reaction of 1 with allyl bromide a mixed- (5) ion produced in the alkylation reaction. The mixed-halide carbene is converted entirely to the chloro carbene over a period of 25 hr in the presence of an excess of bis(tripheny1-phosphine)iminium chloride, [(CsHs)3P]zNCl, in acetonitrile at 25'.…”