Redistribution, ligand

Sm(DippForm)2(THF)2 is isomorphous with the related strontium and barium amidinates. The trivalent samarate complex [Na(THF)5][Sml2(Dipp-Form)2(THF)2] was isolated in small quantities as a colorless by-product. Dissolution of this compound in hexane led to ligand redistribution to give homoleptic Sm(DippForm)3 with concomitant precipitation of Nal and SmlsfTHFls.s. The monofluoro-bis(amidinate) SmF(DippForm)2(THF) could also be isolated from Sm(DippForm)2(THF)2. ... 

Solutions of the alkyl derivatives [TpMe2MgR are generally stable at room temperature. However, heating to 80-120°C results in ligand redistribution, analogous to the Schlenk equilibrium, and the formation... 

The less sterically demanding alkyl derivative [TpMe2]ZnMe is more reactive than [TpBu ]ZnMe towards a number of reagents, e.g., Br2,12, MeOH, PhOH, Bu OOH, Mel, BrCN, and HC1. However, as a result of ligand redistribution, in each case the major product of the reaction is the six-coordinate sandwich complex [TpMe2]2Zn [Eq. (13)] (80, 89). 

Related to the zinc hydroxide complexes [TpRR]ZnOH, the hydrosul-fido complex [TpBut]ZnSH has been synthesized by the reaction of [TpBut]ZnH with H2S (80). However, the corresponding hydrosulfido complex [TpPh]ZnSH was not isolated from the reaction of the less sterically demanding derivative [TpPh]ZnBul with H2S, which gave preferentially the sandwich complex [TpPh]2Zn because of ligand redistribution (81b). 

Ph3P)Au]+ units were also found to be attached side-on to complexes with [(CO)5ReC=CRe(CO)s] units. These adducts may undergo ligand redistribution to give the homoleptic ions.92... 

The combination of equimolar amounts of tris(trimethylsilyl)methyllithium and zinc bromide in a THF/diethyl ether mixture, Scheme 27, furnished tris(trimethylsilyl)methylzinc bromide, as a lithium bromide/ether adduct.43 The compound, which may also be formulated as a lithium alkyldibromozincate, showed no ligand redistribution reactions. It is monomeric in solution and can be treated with 1 equiv. of an organolithium reagent to afford heteroleptic diorganozinc compounds. 

Only two compounds containing Au-In bonds have been structurally characterized to date. They were prepared following reactions which include ligand redistribution and redox processes. Thus, the treatment of Au(PPh3)Cl with InCl (molar ratio 1 1) in THF leads only to isolation of (THF)2Cl2In-InCl2(THF)2 and no gold species were... 

These reactions can also be called ligand redistribution reactions and may be classified by the general equation (83). 

In general M and M may differ or be the same and X may be NR2, OR, a halide, SR, S, 0, etc. The use of Group I metal amides in the synthesis of other metal amides (equations 12-19) provides one class of this type of reaction. A four-center transition state can in most cases be invoked and in studies of the ligand redistributions between Ti(NMe2)4 and Ti(OR)4 compounds (R = Bu and Pr ) activation parameters are consistent with this view.226,227... 

Baney, R. H., and Shindorf, R. J., Electronic effects on ligand redistribution between RR R"SiCl and MeaSiNMe2, 7. Organometal. Chem., 6, 660 (1966). 

Alkylated rare-earth metal complexes with rare-earth metal centers surrounded exclusively by oxygen donor ligands were reported from facile ligand redistribution processes in 2,6-dimethylphenolate/trialkylaluminum mixtures. As shown in Scheme 29 for the yttrium derivatives Y(0ArMe,II)2[(//-OArMe>H)2AlR2](THF)2 (R= Me, Et), heterobimetallic 1 1-species were ac-... 

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