<b>On the Origin of Hydrogen in Metal Hydride Complexes Formed by Reaction With Alcohols</b>

Vaska, L.; DiLuzio, John W.

doi:10.1021/ja00883a081

Cited by 60 publications

(18 citation statements)

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“…This type of reaction has been reported for both iridium (1) and iridium(II1) complexes but not for Vaska's complex itself (22). In agreement, we ourselves have observed no reaction between Vaska's complex and either ethanol or isopropanol under a variety of conditions.…”

Section: Resultssupporting

confidence: 90%

Cationic Aryltetrazene Complexes of Iridium

Gilchrist¹,

Sutton²

1974

Can. J. Chem.

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The details of the synthesis and properties of a number of cationic iridium aryltetrazene complexes of general formula [Ir(CO){N4(C6H4R)2}(PPh3)2]+ where R = H or para-F, Cl, Br, CF3, or OCH3 are presented. The complexes are compared with a number of other compounds possessing tetrazene or tetraazadiene ligands. A possible mechanism of formation is presented, consistent with presently available evidence.

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Section: Resultssupporting

confidence: 90%

Cationic Aryltetrazene Complexes of Iridium

Gilchrist¹,

Sutton²

1974

Can. J. Chem.

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“…On the other hand, a high electron affinity of the titanium also allows an undesirable side reaction to take place; this reaction is indicated by the reaction sequence (20) to (23) in Scheme 5. The @hydrogen…”

Section: Oligomerization Of Ethylene (1-olefins)mentioning

confidence: 99%

Influence of Ligands on the Activity and Specificity of Soluble Transition Metal Catalysts

Henrici‐Olivé¹,

Olivé²

1971

Angew. Chem. Int. Ed. Engl.

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“…Moreover, such abstraction has been observed in molecules having atoms other than carbon in the cr position (12, 13) although it is uncertain from the data in the cases cited if decomposition occurs in the liquid or solid. Related exam~les can be found elsewhere in transition metal chemistry, such as the formation of iridium hydrides from alcohols (14). Abstraction from coordinated diethvl ether offers this pathway in samples A to E: Such a mechanism explains why deuterium is obtained from the ether but never from the alkane.…”

Section: An Alternative Mechanism For Diethyl Ethermentioning

confidence: 89%

The Influence of Coordinating Solvents on the Thermal Decomposition of Methyl Titanium Trichloride

McCowan¹

1973

Can. J. Chem.

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The mechanism of decomposition of CH3TiCI3 in coordinating solvents is shown not to involve free radicals in some cases. An analysis of published work on the decomposition of titanium alkyls suggests mechanisms of decomposition similar to those postulated for alkyls of other transition metals.On demontre que dans certain cas le mecanisme de decomposition du CH3TiC13 dans des solvants coordinants n'implique pas de radicaux libres. Une analyse des resultats publies sur la decomposition des alkyl titanium suggere que leurs mkcanismes de dCcomposition sont similaires a ceux des derives alkyles des autres metaux de transition.[Traduit par le journal]Can. J . Chern.. 51. 1083 (1973) A free radical mechanism of thermal &corn-from Stohler Inc., and from Wilmad Co.Inc.,respectively, position is widely accepted for many alkyl -and were used as received. Non-deuterated solvents were purchased in reagent grade and were distilled under transition metal compounds 2), Particularly the middle cut being used. Both ethers were[ those involving methyl groups. In the particular first refluxed over sodium. case of CH3TiCI,, there is conclusive evidence (3) that free radicals do not form in non-co-Preparatiof2 of CH3TiC13All steps of the preparation were carried out within a ordinating solvents but it has become accepted box of dry nitrogen.(4) that a free radical mechanism is predominant (cH,),~, (3.1 x m01) was added slowiy to a in coordinating solvents. Such a mechanism was solution of 6.2 x mol of TiCI4 in 5 ml of CC13F at originally proposed (5) on the basis of mass about 0°C. After a few minutes shaking as the solution balance considerations and of the relatively fast warmed to room temperature, the precipitated zinc chloride was filtered off. Three 1 ml amounts of CC13F decompositions in coordinating solvents, and it were used to wash remaining CH3TiC13 solution from the was given substantial support by the observation preparation vessel and the filter.(6) that the decomposition kinetics are firstUsing ungreased ground glass joints to prevent reacorder, and that CH,D is among the products, tion, a vacuum trap-to-trap distillation at -35" separated the CH3TiC13 from the more volatile CC13F. The purple when the is carried O u t in a mixed crystals were then dissolved in the working solvent o r solvent tetrahydrof~lran and perdeuterotoluene. transferred directly to the reaction vessel. Precipitation The observation of unambiguous first order techniques of the sort usually employed (3,4,7) invariably kinetics is consistent with the postulate that the result in the occlusion of some solvent (even heptane) in the CH3TiC13 crystals and were therefore unsatisfactory breaking Of the bond for the work in this paper. Two or three distillations are is the rate determining step. Moreover, the exis-required where complete solvent removal is obligatory. tence of CH3D among the products tended to confirm that a radical had formed, capable of Deco~71positiot1 Strldies and ~esrrlts attacking toluene-d, molecules were, A series of decomposi...

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On the Origin of Hydrogen in Metal Hydride Complexes Formed by Reaction With Alcohols

Cited by 60 publications

References 1 publication

Cationic Aryltetrazene Complexes of Iridium

Cationic Aryltetrazene Complexes of Iridium

Influence of Ligands on the Activity and Specificity of Soluble Transition Metal Catalysts

The Influence of Coordinating Solvents on the Thermal Decomposition of Methyl Titanium Trichloride

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