Thiocarbonyl complexes preparation

Carbon monosulfide is not a stable molecule, but carbon monosulfide complexes (more commonly called thiocarbonyl complexes) are known for most of the transition metals. Because of the mstability of free CS, most CS complexes have been prepared by generation of CS from CS, Cl CS, or EtOC(S)Cl in the coordination sphere of the metal, as shown in Equations 2.5, 2.6, and 2.7. Thiocarbonyl ligands vibrate between 1160 and 1410 cm" free CS (in a matrix) vibrates at 1274 cm". A detailed analysis of force constants of mixed carbonyl and thiocarbonyl complexes indicates that the CS ligand can be a weaker or stronger TT-acceptor tiian CO. Seleno- and tellurocarbonyl complexes are also known. ... 

The associative substitution reactions of metal carbonyls, and the preparations, bonding and reactivity of thiocarbonyl complexes were also reviewed in 1985. 

Cyclopentadienyl Carbonyl and Related Complexes.—Successive attack of CHs and CH3+ on [CpMn(CO)2(N2>] yields the azomethane complex [CpMn(CO>2 N-(Me)=NMe ], which can also be synthesized by oxidation of [CpMn(CO)2 MeN-(H)NHMe ]. Similar nucleophilic and electrophilic attacks on the dinitrogen complex using Ph and H+ gives [CpMn(CO)a N(Ph)=NH ]. The pyrrolyl nitrogen atom of [(> -C4H4N)Mn(CO)3] acts as a donor in the formation of the complexes [(OC)3Mn( -C4H4N)M(CO)2Cp] (M = Mn or Re).i The adducts RsP.CSa (R=Bu or Cy) have been assessed as reagents for the preparation of thiocarbonyl complexes. Unfortunately reactions such as [CpMn(CO)2(as-cyclo-octene)] with R3P,CSa lead mainly to [CpMn(CO)2(PR3)] with very low yields of [CpMn(CO)2(CS)].i ... 

Alkylation of thioacyl ligands provides a route to thiocarbene complexes. Faraone and co-workers have prepared iridium thiocarbene complexes 20 and 21 by methyl iodide addition to Ir(I) thiocarbonyl... 

The preparations of several (arene)(thiocarbonyl)chromium(0) complexes bearing electron-donating and/or electron-withdrawing substituents on the ring are described here (A-E). This type of compound is useful in organometallic chemistry for problems related to stereochemistry around a chromium atom6 and in organic chemistry in the activation of arene substituents with respect to alkylation.7... 

The complex (197) with a dithiocarboxylate ligand coordinated to platinum(II) bonded through both monodentate carbon and die chelating dithiocarboxylate ligand has been prepared from either the thiocarbonyl platinum(II) precursor or the carbon disulfide adduct of platinum(O).1796,1797 A cyclopentadienyl-substituted dithiocarboxylate ligand (198) can be used to prepared S,S-bonded platinum(II) and (IV) complexes Pt(C5H4CS2)2 and PtfCsKtCS 2-. The complexes show v(PtS) at 340 cm-1, and in each case electronic absorption bands of the Pt— L type are at 19 500 cm-1 and 29 500 cm-1.1798... 

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