Thiolates organometallics

Bardaji, M., Laguna, A., Perez, M.R. and Jones, P.G. (2002) Unexpected Ring-Opening Reaction to a New Cyanamide-Thiolate Ligand Stabilized as a Dinuclear Gold Complex. Organometallics, 21(9), 1877-1881. 

The cell is suitable for the manufacture of (i) metal alkoxides, (ii) thiolates, (iii) carboxylates, (iv) hydroxides, (v) organometallics and chemicals such as diphenylacetic acid, (vi) ortho- and para-trifluoromethyl-benzoic acid, (vii) aryl-... 

Heterocycles treated in this section belong to several structure types. The metal atoms in compounds under discussion can exist not only in the tetravalent but also in the carbenoid divalent state and the heterocycles differ not only in the nature and number of metal atoms but also in the nature of ring bonds of the latter. Thus, besides conventional organometallic compounds having only M—C bonds there are heterocycles with M—M bonds and those with C—M—X or X—M—Y fragments (X and Y—common heteroatoms like O, S, N). The last type is the most numerous and important group of five-membered Ge-, Sn- and Pb-heterocycles in which the metals are involved in M—X and M— Y bonds similar to those in respective metal alkoxides, thiolates and amides. This feature not only affects the structural parameters of these compounds but determines their chemical properties, synthetic routes and applications. 

Other electrochemically characterized organometallic V(IV) complexes are rare. The thiolate bridged [Cp(CO)2V(/o,-SR)2V(CO)2Cp] (R = Me, Ft, Ph) have reversible reduction processes that range from —1.89 to —2.01 V versus Cp2Fe/THF in addition to two other irreversible reduction processes at more negative potentials. For R = Me, an oxidation at —0.20 V versus Cp2Fe/THF is reported. Reductive bulk electrolysis results in the decomposition of [Cp CO)2V(fi-SMe)2V(CO)2Cp] by loss of SMe [62]. 

Metal thiolates, thiocarbonates and dithiocarbonates are good precursors to prepare sulphides such as CdS and ZnS. A variety of organometallic precursors (usually metal alkyls) have been employed to prepare semiconducting materials (e.g. GaAs, InP). 

Hu W, Luo Q, Ma X, Wu K, Liu J, Chen Y, Xiong S, Wang J, Sadler PJ, Wang F (2009) Arene control over thiolate to sulfinate oxidation in albumin by organometallic ruthenium anticancer complexes. Chem Eur J 15 6586-6594... 

Compounds U(NR2)j and U(OR)j have been synthesized in oxidation states +3 to +6 (though the hexavalent amides are not well characterized). A limited number of thiolates U(SR)4 are also known. These largely molecular species occupy a borderline between classical coordination chemistry and organometallic chemistry. 

The chemistry of iron vinylidene complexes is dominated by the electrophilicity of the carbon atom adjacent to the iron organometallic unit. While addition of water leads to an acyl complex (i.e., the reverse of the dehydration shown in equation 10), addition of an alcohol leads to a vinyl ether complex. Similarly, other iron vinyl complexes can be prepared by the addition of thiolate, hydride, or an organocuprate (Scheme 33). " The nucleophilic addition of imines gave enaminoiron intermediates that could be further elaborated into cyclic aminocarbenes. This methodology has been used to provide access to /3-lactams and ultimately penicillin analogs, and good diastereoselectivities were observed (6 1-15 1) (Scheme 34). 04 Iso, vinylidene complexes are intermediates in cyclizations of alkynyl irons with substituted ketenes, acid chlorides, and related electrophiles an example is shown (equation 11). These cyclizations led to the formation of a series of isolable and characterizable cyclic vinyl iron complexes. 

Four oxidation states of palladium are encountered in organometallic chemistry see Palladium Inorganic Coordination Chemistry) In order of importance, they are Pd , Pd , Pd, and Pd . With the reduction of palladium from Pd to Pd , the metal changes its reactivity from electrophile to nucleophile. However, unlike main group nucleophiles such as thiolates or cyanide, Pd complexes react with both alkyl halides and aryl or vinyl halides. Reactions of Pd complexes with these latter sp halides generate new Pd aryl or vinyl bonds through the process of oxidative addition. 

For organometalloid/organometallic compounds of arsenic, antimony and bismuth, all of the available directly determined enthalpies of formation are shown in Table 1, together with an indication of the experimental method used to obtain them and the appropriate literature references. Also included in Table 1 are the available enthalpy of formation data for the homoleptic hydrides, alkoxides and thiolates, respectively, because ... 

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