Diyl complexes

Table 7.13 Calculated BDEs De (Do) (kcal/mol) of homoleptic iron and group-10 transition metal diyl complexes. ...

Alkynyl ligands are only modest 7i-acids however, this can allow electronic communication between metal centres bound to bis(alkynyl)diyl bridging ligands, e.g. the diruthenium butadiyne-l,4-diyl complex shown (Figure 4.19) undergoes four single 1VE oxidations. If the metals were not in electronic communication, oxidation of one iron centre would not significantly affect the redox potential of the second, i.e. both would oxidize at the same potential. 

In contrast, isoprene undergoes tail-to-tail dimerization upon reacting with RuClg and an excess of isoprene in ethanol to give a chloro-bridged 2,7-dimethylocta-2,6-diene-l,8-diyl complex, [RuCl(a-Cl)(i i7 -CioHi6)]2 [19], which exists in solution as a... 

The group-13 diyl complexes are an example where quantum chemical studies determined the understanding of the metal-ligand bonding situation since the very first compound of the new class of molecules (CO)4Fe-AlCp was isolated and characterized by X-ray structure analysis [93]. The TM-ER bonding situation can be qualitatively... 

Addition of two equivalents of ethynylferrocene to [MCl2(PR3)2] in the presraice of copper(I) iodide and diethylamine produces bis(acetylides) there is some evidence for interacdmi of the palladium or platinum and the iron centres from UV-visible spectroscopy. 36 j je bridging ethyne-diyl complex [PdCl(PR3)2]2(p-CsC) (R = Et, Bu) reacts with phenylisonitrile by double insertion at one of the metal centres producing [PdCl(PR3)2](p-CsCC =NPh C =NPh))[PdCl(PR3)2]. In the presence of 0.2 equivalents of added phosphine ligand the insertions occur symmetrically, one at each metal centre. The crystal structure of the triethylphosphine containing product was rtetermined. The use of two equivalents of added phosphine ligand produces the symmetrical dication [Pd(PR3)3](p-C =NPh CsCC =NPh )[PdCl(PR3)2] [C1]2.137... 

Fig. 1 Synthesis of homo- and heteronuclear group 13-diyl complexes with group 13 Lewis acidic orgcuiometallics...

The ethyne-l,2-diyl complexes [(Ru(CO)2(ri-C5H4R) 2(iLi-C = C)] (R = H, Me) have been employed for the template synthesis of higher nuclearity clusters, air-sensitive [Ru4()i4-C2)(CO)io(r -C5H4R)2] (94) being isolated from reaction with [Ru(CO)4(T3 -C2H4)]. ... 

Complexes 15 and 16 containing a,a-(diphenylphosphino)allyl ligands are formed from thermolysis of the corresponding allyl species 14, whereas, heating 17 affords the hexa-l,3,5-triene-2,6-diyl complex 18. ... 

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