Thioformaldehyde complexes

A thioformaldehyde complex of titanium (55) was similarly obtained from the titanocene methylene complex 54 and either elemental sulfur or sulfur sources such as propene sulfide, cyclohexene sulfide, styrene sulfide, or Ph3P = S. Best yields were achieved with propene sulfide [Eq. (II)].67... 

The reduction of 86 by sodium hydrido borate afforded the dithioformate complex 87 in addition to small amounts of the thioformaldehyde complex 88 (5%).200 201 By modification of the procedure the low yield of 88 could be raised to 25%. Neutral complexes related to 86 form isolable adducts with BH3 (see 90).202 Based on this observation a mechanism was proposed that involves initial formation of the BH3 adducts (89a and 89b) (Scheme 23).201... 

Roper and Town explain the conversion, with hydrogen, of an osmium-coordinated CS ligand in 94 to SMe in terms of successive hydride transfers from the metal to the thiocarbonyl ligand yielding first a thioformaldehyde complex and then a methanethiolate complex, 95 (95). Later this group... 

The electrophilic reactivity of [W=CH2(Tp )(CO)(PhC=CMe)]-[PF ] was tested with both neutral nucleophiles and anionic nucleophiles to give [W-CH2-Nu(Tp )(CO)(PhC=CMe)]+-0. The phthalimide and diethyl malonate derivatives were structurally characterized. Reaction of [W=CH2(Tp )(CO)(PhCsCMe)][PFg] with cyclohexene sulfide produces a sulfur atom transfer to form a tt-bound thioformaldehyde complex. The structure of [W=CH2(Tp )(CO)(PhC=CMe)][BArF] has also been reported.148... 

The reaction of [p-MeC6H4C(NSiMe3)2]2Ta( = CH2)CH3 with 2,6-dimethyl-phenyl isocyanide afforded an f/ -ketenimine complex (Scheme 118). Carbon-sulfur cleavage reactions produced tantalum thioformaldehyde and tantalum sulfido complexes. ... 

Most of the research on thioformaldehyde derivatives has been done on other products formed from formaldehyde and hydrogen sulfide. This reaction is quite complex and gives in addition to methanedithiol and bis(mercaptomethyl)sulfide, trithiane, thioformaldehyde oligomers, and poly(thioformaldehyde). 

Similar results were obtained with [(CO)2(PH3)2Fe(772-E=CH2)]. For E = S a substantially larger binding energy and a more pronounced deformation of the H2C=E ligand was calculated than for E = O. It was concluded that the 77-back-donation is the main bonding interaction between the metal and the H2C=E molecule in the complexes. In the case of the thioformalde-hyde complex, a nonnegligible ligand-to-metal interaction between thioformaldehyde and iron exists.41... 

Several modes of reactions were observed when heterocarbonyl complexes were exposed to oxidizing or reducing agents. The oxidation of the thioformaldehyde ligand in the osmium complex [OsCl(NO)(i72-S = CH2) (PPh3)2]53 with m-chloroperbenzoic acid afforded the rf-S,C complex of the unsubstituted sulfine H2C=S = 0, a molecule that is unknown in the uncoordinated form.226,227... 

In contrast, the related T -thioformaldehyde titanocene complexes 55 [see Eq. (11)] did not give clean insertion products with various triple (C=C and C=N) and double (C=0, C=N, C=S) bonds.67... 

Cobalt, cyclopentadienyl complexes with thioformaldehyde, 55, 14 Cocaine analogs, isoxazolines, 60, 297 Coenzyme factor 420, synthesis, 55, 192 Colloidal media, iodination of pyrazoles in. 57, 344... 

The formation of the thione complex 211 involves the coupling of two thioformaldehyde units, addition to the carbyne carbon of 210 to form a thiocarbene ligand, sulfur insertion into the metal-carbene bond, and... 

A dithiocarbamate ligand acts as the source of sulfur, and its counterion, [H2NEt2], provides a proton in the reaction of the carbyne complex 270 (R = Me, Ph) with [H2NEt2][S2CNEt2]. The proton in 271 is bonded to the carbon of the former carbyne ligand, which has been converted to a thioformaldehyde ligand (181). 

Os3(//-H)2(CO)9(PMe2Ph)], however, the cluster molecule transfers both its hydrides to the CS2, and a C—S bond is cleaved to produce a cluster complex (325) containing a bridging thioformaldehyde and an inorganic sulfide (212). The other product from this reaction is the bridged dithioformate complex 326. When the concentration of the starting material in the... 

MULTIMODE has been applied to a substantial body of molecules and complexes including H2O and HO2 where J greater than zero was considered and treated exactly and approximately [44], to CO-Cu(lOO) [25,45], NHf [46], NH3 [47,48], benzene [49], CFH2O [50], H5O2 [51,52], thioformaldehyde [53], furan, pyrrole, and thiophene [54], and cis and tmns-KOCO [55]. The code has also been used to obtain vibrational energies at transition states [56,57], which are usually done in the harmonic approximation. MM-SR has been adapted to obtain IR spectra and applications have been made to H2O [58], furan, pyrrole, and thiophene [59]. 

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