Ortho-metalated complexes

K. Dedeian, P.I. Djurovich, F.O. Garces, G. Carlson, and R.J. Watts, A new synthetic route to the preparation of a series of strong photoreducing agents fac tris-ortho-metalated complexes of Iridium (III) with substituted 2-phenylpyridines, Inorg. Chem., 30 1685-1687 (1991). 

The first application of phase transfer catalysis in metal carbonyl chemistry was reported by Alper in 1977(23). It was found that metal carbonyl anions could be readily generated by this technique and used to prepare pi-allyl, cluster, and ortho-metalated complexes(24). 

Fig. 25 Pt(II) complex 36 as the first and unique example of a doubly ortho metalated complex with coordination mode III...

Dinuclear complexes of the type [RuH(X)L2]2 (X = C1, Br L = PPh3, AsPh3) are reported to hydrogenate the C=C bond of acrylamide.18 The stoichiometric reaction of (3) with an alkene leads to the ortho-metallated complex (5).19... 

Metallacyclopentenes, in enyne carbometallation, 10, 324 Metallacyclopropanes, with Ti(IV), 4, 359 Metalladiboranes, with Groups 8 and 9, 3, 157—158 2-Metalla-l,3-dichalcogena-[3]ferrocennophanes, Rh complexes, electrochemistry, 7, 149 Metallaoxiranes, preparation, 4, 917 Metallasilazanes, preparation and characteristics, 3, 450 Metallasiloxanes, preparation and characteristics, 3, 458 Metallate(III) compounds, isolated, preparation, 4, 751 ortho-Metallated complexes... 

Sulfur-donor ligand ortho-metalated complexes [e.g., 67] are not only complexes of considerable structural interest, but are of genuine utility in... 

This reaction proceeds readily with metal ions such as Fe1 or Cu in the gas phase.143 The forward reaction is catalyzed, for example, by PdCl2(norbomadiene) while the norbomadiene — quadricyclane photoisomerization is sensitized by an Irm ortho-metallated complex, [(bipy)2Ir(2,2 -bipyrid-3-yl-C3,N1)]2+. 

The isomerization of 2-allylphenol 121 to 2-propenylphenol 122 catalyzed by the ortho-metallated complex Rh[P(OPh)3]3[P(OPh)2(OCeH4)] produces only one isomer (equation 54) °". ... 

In some cases, a second product was also formed in the synthesis. This was identified as a CH activated or ortho-metalated complex (N,0)Ni-(o-Ph)PPh2= CH2, where an ortho C-H bond of a phosphorane phenyl group was deprotonated by the Ni-Me moiety with concomitant formation of methane. Fig. 3.10 shows the molecular structure of complex 132 obtained from ligand 114. The central square planar Ni atom is part of two five-membered metallacycles. 

Sodium or magnesium amalgam reduction of [RuCl2(PPh3)4] in MeCN affords the ortho-metallated complex [RuH(C6H4PPh2XNCMeXPPh3)2]... 

In group 10 we find probably the largest collection of metallomesogens, mainly due to the large collection of ortho-metallated complexes of palladium(ii), which have been exploited by several scientists. 

Photochemical reactions of Ru3(CO)i2 and Os3(CO)i2 with nitrogen hetero-cycles have been studied, with substitution products being formed in most cases. For example, with pyridine the ruthenium compound forms the ortho-metallated complex Ru3H(CO)i i(CsH4N), while the osmium compound gives the simple substitution product Os3(CO)n(py). The novel dihydrido triruthenium cluster H2Ru3(CO)io can be synthesized by photolysis of Ru3(CO)i2 under an atmosphere of dihydrogen. 

Table 80 Thermotropic behavior of the ortho-metallated complexes (250) to (253).

A number of ortho-metallated complexes of ruthenium have been... 

As a bidentate ligand, 2,2 -bipyridine chelates through the two nitrogen centers (1). While this is true for most of the transition metals, stable complexes with C,N -coordination (2) are also formed with metal ions such as Ir(III), Pt(II) and Pd(II). Stable ortho-metalated complexes are also obtained with other ligands such as 2-phenyl pyridine. These ortho-metalated complexes are emissive in fluid solutions and exhibit rich photochemistry. 

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