A study of sulfur ligand reactivity in dimeric dithiolate complexes of vanadium and tungsten

Binuclear CpV, Cp*V, and Cp*Ta Complexes containing Organochalcogenolato Bridges, μ-ER (E = Sulfur, Selenium, Tellurium; R = Methyl, Phenyl, and Ferrocenyl)

“…Following the initial report by Stone and coworkers [18] in 1963, some examples such as [CpV(l-SMe) 2 ] 2 (4 d) [18,19,10] and [CpV(l-SPh) 2 ] 2 (7 d) [20,21,22,10] [24] have been studied with respect to the nature of their metal-metal interaction [20,21,23]. One organoselenido-bridged complex, [CpV(l-SePh) 2 ] 2 (8 d), had also been characterized [20,21].…”

“…In contrast to the carbonyl-containing vanadium(II) complexes, [Cp () V(CO) 2 (l-ER)] 2 , the fully decarbonylated vanadium(III) compounds [Cp ( ) V(l-ER) 2 ] 2 very probably contain direct metal-metal interactions. Although the (temperature-dependent) magnetic data, reported in the literature for the quadruply bridged dimers [CpV(l-SMe) 2 ] 2 (4 d) [18], [CpV(l-SPh) 2 ] 2 (7 d) [21,22], [CpV(l 2 -SCH 2 CH(R)S)] 2 (R = H, Me) [23] and [CpV(l 2 -SC(CF 3 )=C(CF 3 )S)] 2 [24], are somewhat confusing [cf. 23], they are definitely below the spin-only value of 2.83 l B per vanadium which would indicate two uncoupled vanadium(III) centers.…”

“…23], they are definitely below the spin-only value of 2.83 l B per vanadium which would indicate two uncoupled vanadium(III) centers. Therefore either a direct V±V bond and/or partial antiferromagnetic coupling through the organochalcogenolato bridges has to be assumed [23]. An X-ray structure analysis of [CpV(l 2 -SCH 2 CH 2 S)] 2 [23] revealed a short V±V' contact of 254.2(1) pm and an acute V±S±V angle of 63.4(1)°, which are both consistent with a metal-metal bond.…”

Cyclopentadienyl Complexes of Chromium, Molybdenum and Tungsten

“…991 ' 1073 Like its molybdenum analogue, [W 2 (S) 2 (n-S) 2 Cp 2 ] reacts with acetylene to give the ji-dithiolene complex [W 2 (u-SCH=CHS) 2 Cp 2 ] but the chelating dithiolene complexes [W 2 (S)(u-S) 2 (SCH=CHS)Cp 2 ] and [W 2 (u-S) 2 (SCH=CHS) 2 Cp 2 ] are also formed; the analogous SCH 2 CH 2 S species are available from the reaction of [WH(CO) 3 Cp] with ethylene sulfide. 1074 The reaction of [WH(CO) 3 Cp] with S(NMe 2 ) 2 produces [{W(CO) 3 Cp} 2 (u-S)], which reacts with CH 2 N 2 to give the thioformaldehyde complex [W 2 (CO) 4 (u-SCH 2 )Cp 2 ]. 1075 can also be isolated.…”

Pterins, Quinoxalines, and Metallo-Ene-Dithiolates

“…A limited number of 1,2-ene-dithiolates can be isolated as the disodium salts and many of these contain electron-withdrawing groups (72-77). However, many 1,2-ene-dithiolates can be prepared as metal complexes where the 1,2-ene-dithiolate is stabilized as a chelating ligand (as is suggested for Moco) (18)(19)(20)(21)(22)(23)(24)(25)(26)(27)(28). Synthetic routes to métallo-1,2-ene-dithiolate complexes include the reactions of metal complexes (containing labile ligands) with dithines (26), dithiolium salts (79,29) or ahydroxy ketones in the presence of P4S10 (17), as shown in equations 1, 2, and 3, respectively.…”