Complexes with thiocarbonyl

Little new chemistry of osmium thia-macrocycles has appeared, but both ruthenium and osmium [9]aneS3 complexes with thiocarbonyl ligands and their migratory coupling reactions have been investigated. ... 

The existence of two stereoisomeric complexes with thiocarbonyl [41] and carbonyl bases [42], one planar on the non-bonding sulfur (oxygen) lone pair and the other perpendicular on the sulfur (oxygen) tt electrons. The perpendicular complex is favoured by bulky substituents on the (thio)carbonyl group and by the n character of the HOMO of the... 

An example of thione coordination is demonstrated with the thiocarbonyl donor ligand 2,6-dimethyl-4H-pyran-4-thione, that gives a complex with zinc chloride of the form ZnL2Cl2-The crystal structure shows the zinc is tetrahedrally coordinated by two chloride and two sulfur donors and the compound was further studied by 3H NMR and IR spectroscopy.573 Both monomeric and dimeric heterocyclic thione complexes have been formed with zinc.5 4,575... 

Treatment of Fischer-type carbene complexes with different oxidants can lead to the formation of carbonyl compounds [150,253]. Treatment with sulfur leads to the formation of complexed thiocarbonyl compounds [141]. Conversion of the carbene carbon atom into a methylene or acetal group can be achieved by treatment with reducing agents. Treatment of vinylcarbene complexes with diborane can also lead to demetallation and formation of diols [278]. The conversion of heteroatom-substituted carbene complexes to non-heteroatom-substituted carbene complexes... 

Upon acylation of the copper complex with benzoyl chloride the corresponding 5-benzoylthio-1,2,3,4-thiatriazole is formed. The reaction product is (apparently) incorrectly assigned by the authors to 4-benzoyl-1,2,3,4-thiatriazole-5-thione based upon comparison with the product obtained from direct acylation of thiatriazol-5-thiol and citation of the older incorrect structure assignments. The thiothiatriazolato-copper(I) complexes are formulated as Cu-N(4) complexes. However, this assignment is based upon an IR band at 1200 cm attributed to a thiocarbonyl group, again upon comparison with the older literature. Further characterization therefore seems necessary. 

Copolymers with hexafluorocyclobutanone have been made in ether at low temperatures using cesium fluoride as an initiator. They are of low molecylar weight and are more resistant to amine degradation than the homopolymer. Copolymerization of perfluoroacetahlehyde and perfluoropropionaldehyde with thiocarbonyl fluoride has been accomplished by initiation with complex compounds of the type Me(PR3)BB (67) in which Me is a group VIII metal and B is P(C6Hs)3 or a halogen. The products have excellent resistance to acids. 

Insertion of imsymmetrical heterocumulenes such as 0=C=X (X = S, NR), into an N-Si bond can produce two different constitutional isomers [8]. In the case of compound 1 and X = NR, R = alkyl or aryl, there is rapid insertion into both N-Si functions and the resulting situation is extremely complex with respect to the configurational (0,N-silylation) and conformational isomerism [5, 8, 10]. In contrast, 0=C=S inserts rapidly into only one N-Si bond of 1, there is no evidence for any second insertion even after several days. The formation of small amounts of pyrazine as oxidation product even under strictly anaerobic conditions suggests some electron transfer reactivity. Spectroscopic [10] and especially the structural evidence given below show that of the two conceivable constitutional isomers [11] of the insertion reaction only the 0-Si bonded species 2 with intact thiocarbonyl function is formed. 

Photocyclisation of 2-arylthiocyclohexenones (414) yields racemic dihydrobenzo-thiophenes (416) via a thiocarbonyl ylide (415). Theprochiral compounds (414) also form 1 1 inclusion complexes with the homochiral host (63) and irradiation of crystals of these complexes yields the dihydrobenzothiophenes (416) in 32-83% enantiomeric excess, optically pure samples being easily accessible by further recrystallisation. The decay kinetics for ylides (415), produced by laser flash photolysis of the aryl vinyl sulfldes (414), indicate the presence of more than one ylide species in each case. ... 

TRI-ju-CHLORO-CHLOROTETRAKIS(TRIPHENYLPHOS-PHINE)DIRUTHENIUM(II) COMPLEXES WITH ACETONE CARBONYL AND THIOCARBONYL LIGANDS... 

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