Selenium coordination compounds

Nickel-selenium coordination compounds have received attention in recent years, because a unique Ni-selenocysteine interaction was revealed in the active site of [FeNiSe]-hydrogenases.1083,1084 Of particular interest in this regard are mixed CO/selenolate complexes. Distorted square planar (393) was prepared from [CpNi(CO)]2, PhSeSePh, and [Fe(CO)3(SePh)3] and provides the first example of CO bound to a square planar Ni11 center in thiolate/selenolate environment.1085,1086 Upon addition of RSSR, species of the series [Ni(CO)(SR) (SePh)3 ] are formed. //(CO) ranges from 2,023 cm-1 to 2,043 cm-1 and is regarded as a spectroscopic reference for the CO binding site in [NiFeSe] hydrogenases. 

Ligands Other than Oxygen and Sulfur. See Sec. 3.1.7, Coordination Compounds, for acids containing ligands other than oxygen and sulfur (selenium and tellurium). 

Trialkyl- and triarylarsine sulfides have been prepared by several different methods. The reaction of sulfur with a tertiary arsine, with or without a solvent, gives the sulfides in almost quantitative yields. Another method involves the reaction of hydrogen sulfide with a tertiary arsine oxide, hydroxyhahde, or dihaloarsorane. X-ray diffraction studies of triphenylarsine sulfide [3937-40-4], C gH AsS, show the arsenic to be tetrahedral the arsenic—sulfur bond is a tme double bond (137). Triphenylarsine sulfide and trimethylarsine sulfide [38859-90-4], C H AsS, form a number of coordination compounds with salts of transition elements (138,139). Both trialkyl- and triarylarsine selenides have been reported. The trialkyl compounds have been prepared by refluxing trialkylarsines with selenium powder (140). The preparation of triphenylarsine selenide [65374-39-2], C gH AsSe, from dichlorotriphenylarsorane and hydrogen selenide has been reported (141), but other workers could not dupHcate this work (140). 

Coordination compounds of selenium-containing heterocycles with an Se — M bond are represented by the complexes of 1,4-diselenane 346 348 [634] and seleno-phene 349 [8,643]. Among these complexes, while the Se — M coordination 350 was proposed [634] for the complexes on the basis of 1,2,3-benzoselenodiazole, only N—M binding 351 was found in these compounds [13,644] ... 

Only after the publication of CCC (1987) were well-characterized coordination compounds of the. s-block elements containing bonds to Se or Te described. As a rule selenium or tellurium donor... 

Sulfur, selenium, and tellurium are all capable of forming six-coordinate compounds such as SEg. Give two reasons why oxygen cannot be the central atom in such six-coordinate molecules. 

This volume has been divided (arbitrarily) into seven chapters. Chapter 1 contains some interesting syntheses of sulfur- and selenium-containing coordination compounds and clusters including the synthesis of the [Fe4S4(SR)4]2 species which R. H. Holm so elegantly identified as models for active sites in nonheme iron proteins. Compounds formed from S22 and S52 are described. A convenient synthesis of CSe2 is reported. Several additional compounds relevant to biological sulfur chemistry are described. 

Selenium, bis(diethyldithiocarbamato)-stereochemistry, 60 Selenium, bis(dithiofurancarbamato)-stereochemistry, 60 Selenium(II) complexes bis(dithiochelate), 60 Selenocyanate complexes linkage isomers, 186 Selenonium ions, trifluoro-stereochemistry, 37 Self-exchange reactions, 333 electron transfer rate constants, 347-353, 366 rate constants calculation, 348 rate constants, 362 Semicarbazide, 1,4-diphenylthio-ruthenium determination, 546 Semi-glycinecresol red metallochromic indicator, 557 Semi-xylenol orange metallochromic indicator, 557 Seven-coordinate compounds stereochemistry, 69-83 Sidgwick, Nevil Vincent, 16 Silicon, tris(acetylacetone)-configuration, 195... 

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