“…The key to the formation of 8 and 9 is the dichlorocarbene complex 7 , and dihalocarbene complexes in general undergo many other interesting reactions dependent upon the presence of good leaving groups on the carbene carbon atom . Even coordinatively saturated haloalkyl complexes related to 6 (see complex 11 in Scheme ) exhibit interesting nucleophilic substitution reactions at the metal-bound carbon 2 3 4 …”
Silyl and stannyl complexes of ruthenium and osmium bearing halogen substituents on the silicon and tin atoms undergo many interesting reactions. While there are formal similarities, there are also marked differences between these silyl and stannyl derivatives. This review first surveys the synthetic approaches we have developed to the silyl and stannyl complexes that involve oxidative addition of halogenated silanes coupled with reductive elimination for the preparation of the silyl complexes L n M(SiR n X 3-n ) (M ) Ru, Os) and reaction between L n MH and the vinylstannane R 3 SnCHdCH 2 to give first the triorganostannyl complexes L n M(SnR 3 ) (M ) Ru, Os), which are then functionalized by redistribution reactions to give L n M(SnR n X 3-n ) (M ) Ru, Os). Among the unusual compounds derived from these halogenated silyl and stannyl complexes are derivatives with the following novel ligands: Si(OH) 3 , Sn-(OH) 3 , silatranyl, stannatranyl, SnH 3 , and SnMe 2 SnPh 3 . A contrast between the osmasilanol L n Os(SiMe 2 -OH) and the osmastannol L n Os(SnMe 2 OH) is that the former deprotonates to a silanolate anion, [L n Os(SiMe 2 O)] -, while the latter, when treated with base, ortho-stannylates a triphenylphosphine ligand. Another contrast is provided by the ease with which osmium trimethylstannyl complexes undergo R-methyl migration reactions.
“…The key to the formation of 8 and 9 is the dichlorocarbene complex 7 , and dihalocarbene complexes in general undergo many other interesting reactions dependent upon the presence of good leaving groups on the carbene carbon atom . Even coordinatively saturated haloalkyl complexes related to 6 (see complex 11 in Scheme ) exhibit interesting nucleophilic substitution reactions at the metal-bound carbon 2 3 4 …”
Silyl and stannyl complexes of ruthenium and osmium bearing halogen substituents on the silicon and tin atoms undergo many interesting reactions. While there are formal similarities, there are also marked differences between these silyl and stannyl derivatives. This review first surveys the synthetic approaches we have developed to the silyl and stannyl complexes that involve oxidative addition of halogenated silanes coupled with reductive elimination for the preparation of the silyl complexes L n M(SiR n X 3-n ) (M ) Ru, Os) and reaction between L n MH and the vinylstannane R 3 SnCHdCH 2 to give first the triorganostannyl complexes L n M(SnR 3 ) (M ) Ru, Os), which are then functionalized by redistribution reactions to give L n M(SnR n X 3-n ) (M ) Ru, Os). Among the unusual compounds derived from these halogenated silyl and stannyl complexes are derivatives with the following novel ligands: Si(OH) 3 , Sn-(OH) 3 , silatranyl, stannatranyl, SnH 3 , and SnMe 2 SnPh 3 . A contrast between the osmasilanol L n Os(SiMe 2 -OH) and the osmastannol L n Os(SnMe 2 OH) is that the former deprotonates to a silanolate anion, [L n Os(SiMe 2 O)] -, while the latter, when treated with base, ortho-stannylates a triphenylphosphine ligand. Another contrast is provided by the ease with which osmium trimethylstannyl complexes undergo R-methyl migration reactions.
“…Complexes of this type, for example, 43 and 45, have been prepared as blue crystalline compounds by treatment of the manganese complexes 42 41 or 44 42 with diazoalkanes. 41,43 The reactions of osmium complexes 46 44 and 47 45 with hydrogentelluride anions 44 or elemental tellurium 45 resulted in the formation of telluroformaldehyde complexes 48a,b.…”
Section: D Sadekovmentioning
confidence: 99%
“…43 In the reaction with methyl iodide, the attack is directed at the tellurium atom; the cationic complex 50 thus formed is easily reduced by sodium tetrahydridoborate with opening of the three-membered ring to give complex 51. 44 Rhodium complexes 53 containing rigid three-membered rings have been synthesised in relatively low yields by reaction of rhodium complexes 52 with sodium hydrogentelluride. 46,47 Te…”
Data on the methods of synthesis, structures, and reactivity of organic derivatives of monocoordinated tellurium, namely, compounds with C=Te bonds and phosphine tellurides R 3 P=Te, are described systematically and generalised. The use of the latter compounds as synthetic equivalents of elemental tellu rium for the preparation of metal tellurides is considered. The bibliography includes 139 references.
“…Due to the difficulty in their preparation, the ligand properties of tellurocarbonyls have not been well explored. A few metal complexes in which telluroaldehydes [7][8][9][10][11][12], telluroketones [13][14][15], and telluroureas [16,17] function as ligands have been reported. To date, however, no example in which a telluroamide functions as a ligand has appeared in the literature.…”
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